Preparation of polymeric resins and carbon materials

ABSTRACT

The present application is directed to methods for preparation of carbon materials. The carbon materials comprise enhanced electrochemical properties and find utility in any number of electrical devices, for example, as electrode material in ultracapacitors or batteries.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation application of U.S. patentapplication Ser. No. 17/860,011, filed Jul. 7, 2022, which is acontinuation application of U.S. patent application Ser. No. 15/199,318,filed Jun. 30, 2016, now U.S. Pat. No. 11,401,363, which is acontinuation application of U.S. patent application Ser. No. 13/763,448,filed Feb. 8, 2013, now U.S. Pat. No. 9,409,777, which claims priorityto U.S. Provisional Application No. 61/597,121, filed Feb. 9, 2012, thedisclosure of which, along with all documents cited therein, isincorporated by reference in its entirety.

BACKGROUND Technical Field

The present invention generally relates to novel methods for preparingpolymeric resin materials and preparation of carbon materials from thesame.

Description of the Related Art

Activated carbon is commonly employed in electrical storage anddistribution devices. The surface area, conductivity and porosity ofactivated carbon allows for the design of electrical devices havingdesirable electrochemical performance. Electric double-layer capacitors(EDLCs or “ultracapacitors”) are an example of such devices. EDLCs oftenhave electrodes prepared from an activated carbon material and asuitable electrolyte, and have an extremely high energy density comparedto more common capacitors. Typical uses for EDLCs include energy storageand distribution in devices requiring short bursts of power for datatransmissions, or peak-power functions such as wireless modems, mobilephones, digital cameras and other hand-held electronic devices. EDLCsare also commonly used in electric vehicles such as electric cars,trains, buses and the like.

Batteries are another common energy storage and distribution devicewhich often contain an activated carbon material (e.g., as anodematerial, current collector, or conductivity enhancer). For example,lithium/carbon batteries having a carbonaceous anode intercalated withlithium represent a promising energy storage device. Other types ofcarbon-containing batteries include lithium air batteries, which useporous carbon as the current collector for the air electrode, and leadacid batteries which often include carbon additives in either the anodeor cathode. Batteries are employed in any number of electronic devicesrequiring low current density electrical power (as compared to an EDLC'shigh current density).

One known limitation of EDLCs and carbon-based batteries is decreasedperformance at high-temperature, high voltage operation, repeatedcharge/discharge cycles and/or upon aging. This decreased performancehas been attributed, at least in part, to electrolyte impurity orimpurities in the carbon electrode itself, causing breakdown of theelectrode at the electrolyte/electrode interface. Thus, it has beensuggested that EDLCs and/or batteries comprising electrodes preparedfrom higher purity carbon materials could be operated at higher voltagesand for longer periods of time at higher temperatures than existingdevices.

In addition to purity, another known limitation of carbon-containingelectrical devices is the pore structure of the activated carbon itself.While activated carbon materials typically comprise high porosity, thepore size distribution is not optimized for use in electrical energystorage and distribution devices. Such optimization may include a blendof both micropores and mesopores. Additionally in some applications ahigh surface area carbon may be desirable, while in others a low surfaceare material is preferred. Idealized pore size distributions canmaximize performance attributes including but not limited to, increasedion mobility (i.e., lower resistance), increased power density, improvedvolumetric capacitance, increased cycle life efficiency of devicesprepared from the optimized carbon materials.

One common method for producing carbon materials is to pyrolyze anexisting carbon-containing material (e.g., coconut fibers or tirerubber). This results in a char with relatively low surface area whichcan subsequently be over-activated to produce a material with thesurface area and porosity necessary for the desired application. Such anapproach is inherently limited by the existing structure of theprecursor material, and typically results in a carbon material having anunoptimized pore structure and an ash content (e.g., metal impurities)of 1% or higher.

Activated carbon materials can also be prepared by chemical activation.For example, treatment of a carbon-containing material with an acid,base or salt (e.g., phosphoric acid, potassium hydroxide, sodiumhydroxide, zinc chloride, etc.) followed by heating results in anactivated carbon material. However, such chemical activation alsoproduces an activated carbon material not suitable for use in highperformance electrical devices.

Another approach for producing high surface area activated carbonmaterials is to prepare a synthetic polymer from carbon-containingorganic building blocks (e.g., a polymer gel). As with the existingorganic materials, the synthetically prepared polymers are pyrolyzed andactivated to produce an activated carbon material. In contrast to thetraditional approach described above, the intrinsic porosity of thesynthetically prepared polymer results in higher process yields becauseless material is lost during the activation step. Although such methodsmay be applicable in laboratory or small-scale settings, preparation oflarge quantities of carbon materials via synthetic polymers may belimited at large scales. For example, the solid polymer gel monolithsgenerally obtained may be difficult to work with (e.g., transfer fromone vessel to another, milling, grinding, etc.) at the scales needed forindustrial applicability, and the exothermic nature of thepolymerization may be difficult to control. Accordingly, methods forpreparation of high grade carbon materials that are applicable to largescale-scale syntheses are needed.

While significant advances have been made in the field, there continuesto be a need in the art for improved methods for preparation of highpurity carbon materials comprising an optimized pore structure for usein electrical energy storage devices. The present invention fulfillsthese needs and provides further related advantages.

BRIEF SUMMARY

In general terms, the current invention is directed to novel methods forpreparation of carbon materials comprising an optimized pore structure.The methods generally comprise preparation of a mixture of polymerprecursors (i.e., a polymer phase) and a continuous phase and allowingthe polymer precursors (e.g., resorcinol and formaldehyde) topolymerize. The mixture may be an emulsion and/or a suspension. Theresulting polymer can then optionally be converted to carbon materialsby any number of post-processing procedures, including pyrolysis and/oractivation. Advantageously, the present inventors have discovered thatthe presently disclosed methods allow for preparation of polymer gels(e.g., condensation polymer gels) and carbon materials at commerciallyrelevant scales, and physical properties such as the pore structure andparticle size of the gels and carbon materials can be controlled throughoptimization of the process parameters (e.g., continuous phaseselections, etc.).

Accordingly, in one embodiment the present disclosure provides a methodfor making polymer particles in gel form via an emulsion or suspensionprocess, the method comprising:

a) preparing a reactant mixture comprising a monomer componentcomprising one or more phenolic compounds, one or more crosslinkingcompounds, and a carrier fluid; and

b) polymerizing the one or more phenolic compounds with the one or morecrosslinking compounds,

wherein the carrier fluid comprises a surfactant in a concentrationequal to or greater than the critical micelle concentration and thevolume average particle size (Dv,50) of the polymer particles is lessthan or equal to 1 mm.

In another embodiment, the disclosure provides a method for makingpolymer particles in gel form via an emulsion or suspension process, themethod comprising:

a) preparing a reactant mixture comprising a monomer componentcomprising one or more phenolic compounds, one or more crosslinkingcompounds, and a carrier fluid; and

b) polymerizing the one or more phenolic compounds with the one or morecrosslinking compounds,

wherein the carrier fluid comprises 50 wt % or more of cyclohexane,based on the total weight of the carrier fluid, and the volume averageparticle size (Dv,50) of the polymer particles is less than or equal to1 mm.

In still other embodiments, the disclosure is directed to a method formaking polymer particles in gel form via an emulsion or suspensionprocess, the method comprising:

a) preparing a reactant mixture comprising a monomer componentcomprising one or more phenolic compounds, one or more crosslinkingcompounds, and a carrier fluid; and

b) polymerizing the one or more phenolic compounds with the one or morecrosslinking compounds,

wherein the carrier fluid comprises 50 wt % or more of cyclohexane,based on the total weight of the carrier fluid, and the volume averageparticle size (Dv,50) of the polymer particles is greater than or equalto 1 mm.

In some embodiments of the foregoing methods, the Dv,50 of the polymerparticles is less than or equal to 0.5 mm. For example, in certainembodiments the Dv,50 of the polymer particles is less than or equal to0.1 mm.

In still other embodiments of some of the foregoing methods, the Dv,50of the polymer particles is less than or equal to 2 mm. For example, incertain embodiments the Dv,50 of the polymer particles is greater thanor equal to 4 mm.

In other embodiments of the foregoing, the carrier fluid comprises oneor more vegetable oils, one or more minerals oils having from about 15to about 40 carbon atoms, one or more chlorinated hydrocarbons, one ormore paraffinic oils, or any combination thereof.

In more embodiments, the monomer component is an aqueous mixturecomprising the one or more phenolic compounds and one or more catalysts.For example, in some embodiments the one or more catalysts comprises anorganic acid. In other embodiments, the one or more catalysts comprisesa volatile basic salt. In still other embodiments, the one or morecatalysts comprises a volatile basic salt and comprises an organic acid.For example, in certain examples the volatile basic salt is ammoniumcarbonate, ammonium bicarbonate, ammonium acetate, or ammoniumhydroxide, or a combination thereof. In other embodiments, the organicacid is acetic acid, formic acid, propionic acid, maleic acid, oxalicacid, uric acid, lactic acid, or a combination thereof. In still moreembodiments, the one or more catalysts contains a total of less than 500ppm moieties comprising arsenic, antimony, bismuth, or ions thereof, ora halogen.

In other embodiments, a molar ratio of the one or more phenoliccompounds to the one or more catalysts ranges from about 5 to about 400.For example, in some embodiments a molar ratio of the one or morephenolic compounds to the one or more catalysts ranges from about 5 toabout 50.

In certain other embodiments of the foregoing methods, the polymerparticles in gel form are made via the suspension process, the reactantmixture is a suspension and the method further comprises agitation ofthe suspension with a mixer.

In some embodiments, the methods further comprise separating the polymerparticles from the carrier fluid to provide separated polymer particlesin gel form.

In other embodiments, the methods further comprise heating the reactantmixture to a temperature ranging from about 30° C. to about 100° C. Inother embodiments, the reactant mixture is at a temperature of about 80°C. or more during polymerization of the reactant mixture. In still otherembodiments, the reactant mixture is at a temperature ranging from about80° C. to about 150° C. during polymerization of the monomer component.

In some more embodiments of the foregoing methods, the reactant mixturehas a pH of less than 7 during polymerization. In some other examples,the reactant mixture has a pH of less than 5 during polymerization. Instill more embodiments, the reactant mixture has a pH of less than 4during polymerization.

In other embodiments, the one or more phenolic compounds and the one ormore crosslinking compounds are prepolymerized with one another to forma prepolymer prior to making the polymer particles in gel form via theemulsion or suspension process.

Other embodiments further comprise admixing a silicon-containingelectrochemical modifier with the polymer precursor mixture, the polymerphase or the continuous phase, and other embodiments further compriseadmixing a nitrogen-containing electrochemical modifier with the polymerprecursor mixture, the polymer phase or the continuous phase. Forexample, in some embodiments the nitrogen-containing electrochemicalmodifier is urea, melamine, or combination thereof.

In certain embodiments of the above, the reaction mixture furthercomprises 0.01% to 20% of a non-ionic surfactant having a molecularweight of from about 100 Daltons to about 2,000 Daltons.

In some other embodiments, the reactant mixture is aged for 12 hours orless at a temperature between about 45 and 70 C. In still moreembodiments, the reactant mixture is aged for 6 hours or less at atemperature between about 45 and 70 C.

In certain embodiments, the polymer gel particles comprise a total porevolume of between about 0.01 and 1.5 cm3/g, and in other embodiments thepolymer gel particles comprise a total pore volume of between about 0.1and 0.9 cm3/g.

In other embodiments of any of the foregoing methods, the methodsfurther comprise pyrolyzing the polymer gel particles by a methodcomprising heating the polymer gel particles in an inert atmosphere attemperatures ranging from 500° C. to 2400° C. For example, in someembodiments the pyrolyzed polymer gel particles have a total pore volumegreater than 0.8 cm3/g and a gerameter (GM) between 9 and 21.

In other embodiments, the methods further comprise:

a) pyrolyzing the polymer gel particles by a method comprising heatingthe condensation polymer gel particles in an inert atmosphere attemperatures ranging from 500° C. to 2400° C., and

b) activating the pyrolzyed polymer gel particles in an atmospherecomprising carbon dioxide, carbon monoxide, steam, oxygen orcombinations thereof at a temperature may ranging from 800° C. to 1300°C. In certain embodiments, the pyrolyzed and activated polymer gelparticles have a total pore volume greater 38. The method according toclaim 37, wherein than 0.6 cm3/g and a gerameter (GM) greater than orequal to 21. In other embodiments, the pyrolyzed and activated polymergel particles have a total pore volume greater than 1 cm3/g and agerameter (GM) ranging from 9 to 21.

In other embodiments, the disclosure provides a polymer gel having aparticle size distribution such that Dv,50 is less than about 1 mm and(Dv,90−Dv,10)/Dv,50 is less than 3, wherein Dv,10, Dv,50 and Dv,90 arethe particle size at 10%, 50% and 90%, respectively of the particle sizedistribution by volume.

In still more embodiments, the disclosure is directed to a polymer gelhaving a particle size distribution such that Dv,50 is less than about0.5 mm and (Dv,90−Dv,10)/Dv,50 is less than 3, wherein Dv,10, Dv,50 andDv,90 are the particle size at 10%, 50% and 90%, respectively of theparticle size distribution by volume.

In even more embodiments, the disclosure provides a polymer gel having aparticle size distribution such that Dv,50 is greater than about 0.1 mmand (Dv,90−Dv,10)/Dv,50 is less than 3, wherein Dv,10, Dv,50 and Dv,90are the particle size at 10%, 50% and 90%, respectively of the particlesize distribution by volume.

In some of the foregoing polymer gel embodiments, (Dv,90−Dv,10)/Dv,50 isless than 2. In other embodiments, (Dv,90−Dv,10)/Dv,50 is less than 1.

Other embodiments of the present disclosure are directed to a carbonmaterial, wherein the maximum theoretical capacitance of the carbonmaterial is greater than 25 F/cm3 as measured at a current density of0.5 Amp/g employing an electrolyte comprising tetraethylammoniumtetrafluoroborane in acetonitrile, and wherein the carbon materialcomprises less than 500 ppm of all atoms having a molecular weightbetween 11 and 92 as measured by photon induced x-ray emissions.

In another embodiment an electrode is provided, the electrode comprisinga carbon material produced according to any one of the methods describedherein or a carbon material described herein (e.g., the foregoing carbonmaterial).

Other embodiments provide an electrical energy storage device comprisinga carbon material produced according to any one of the methods describedherein or a carbon material described herein (e.g., the foregoing carbonmaterial). In some embodiments, the electrical energy storage device isa double layer ultracapacitor. In other embodiments, the electricalenergy storage device is a lithium/carbon battery, zinc/carbon battery,lithium air battery or lead acid battery.

In other embodiments, an electrode comprising carbon is provided,wherein the carbon comprises a maximum theoretical capacitance ofgreater than 25 F/cm3 and wherein the electrode retains greater than 90%of its capacitance after incubation at 2.85 V and 85 C for 32 h, whereinthe capacitance is measured at a current density of 0.5 Amp/g employingan electrolyte comprising tetraethylammonium tetrafluoroborane inacetonitrile.

In other embodiments, the present disclosure provides an electrodecomprising carbon, wherein the carbon comprises a maximum theoreticalcapacitance of greater than 20 F/cm3, wherein the capacitance ismeasured after incubation at 2.85 V and 85 C for 32 h, and at a currentdensity of 0.5 Amp/g employing an electrolyte comprisingtetraethylammonium tetrafluoroborane in acetonitrile. For example, insome embodiments the carbon comprises a maximum theoretical capacitanceof greater than 23 F/cm3 maximum theoretical capacitance, wherein thecapacitance is measured after incubation at 2.85 V and 85 C for 32 h,and at a current density of 0.5 Amp/g employing an electrolytecomprising tetraethylammonium tetrafluoroborane in acetonitrile.

In other embodiments, the disclosure is directed to an electrical energystorage device comprising any one of the above described electrodes. Incertain embodiments, the electrical energy storage device is a doublelayer ultracapacitor.

Polymer gels and carbon materials prepared according to the disclosedmethods and electrodes and devices comprising the carbon materials, arealso provided.

These and other aspects of the invention will be apparent upon referenceto the following detailed description. To this end, various referencesare set forth herein which describe in more detail certain backgroundinformation, procedures, compounds and/or compositions, and are eachhereby incorporated by reference in their entirety.

BRIEF DESCRIPTION OF THE DRAWINGS

In the figures, identical reference numbers identify similar elements.The sizes and relative positions of elements in the figures are notnecessarily drawn to scale and some of these elements are arbitrarilyenlarged and positioned to improve figure legibility. Further, theparticular shapes of the elements as drawn are not intended to conveyany information regarding the actual shape of the particular elements,and have been solely selected for ease of recognition in the figures.

FIG. 1 shows N₂ absorption isotherms for freeze dried gels.

FIG. 2 presents N₂ absorption isotherms for activated carbon samples.

FIG. 3 is a graph showing N₂ absorption isotherms for freeze dried gels.

FIG. 4 demonstrates Pore size distributions for dry gels.

FIG. 5 is a bar graph showing weight loss upon activation.

FIG. 6 shows N₂ absorption isotherms for activated carbon samples.

FIG. 7 illustrates pore size distribution DFT for activated carbons.

FIG. 8 is a graph of pore volume distributions for RD-538 freeze driedgels.

FIG. 9 presents N₂ absorption isotherms for activated carbon samples.

FIG. 10 shows pore size distributions for activated carbons.

FIG. 11 presents pore volume distributions for freeze dried gels.

FIG. 12 is a graph of pore size distributions for activated carbons.

FIG. 13 shows nitrogen absorption isotherms for activated carbonsamples.

FIG. 14 is pore size data for activated carbon samples.

FIG. 15 presents nitrogen absorption isotherms for activated carbonsamples.

FIG. 16 is a graph of nitrogen absorption isotherms for freeze driedgels.

FIG. 17 shows nitrogen absorption isotherms for activated carbonsamples.

FIG. 18 presents pore size distributions for activated carbons.

FIG. 19 illustrates TGA data for a urea-formaldehyde emulsion.

FIG. 20 shows electrochemical performance of a urea-formaldehyde basedcarbon material.

FIG. 21 depicts electrochemical performance of a silicon-carboncomposite material.

FIG. 22 shows particle size distributions for gels and carbon materials.

FIGS. 23A and 23B are pictures showing spherical gel particles andspherical carbon material particles, respectively.

DETAILED DESCRIPTION

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments.However, one skilled in the art will understand that the invention maybe practiced without these details. In other instances, well-knownstructures have not been shown or described in detail to avoidunnecessarily obscuring descriptions of the embodiments. Unless thecontext requires otherwise, throughout the specification and claimswhich follow, the word “comprise” and variations thereof, such as,“comprises” and “comprising” are to be construed in an open, inclusivesense, that is, as “including, but not limited to.” Further, headingsprovided herein are for convenience only and do not interpret the scopeor meaning of the claimed invention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment. Thus, the appearances of the phrases “in one embodiment” or“in an embodiment” in various places throughout this specification arenot necessarily all referring to the same embodiment. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments. Also, as used in thisspecification and the appended claims, the singular forms “a,” “an,” and“the” include plural referents unless the content clearly dictatesotherwise. It should also be noted that the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

Definitions

As used herein, and unless the context dictates otherwise, the followingterms have the meanings as specified below.

“Carbon material” refers to a material or substance comprisedsubstantially of carbon (e.g., >90%, >95%, greater than 99% or greaterthan 99.9% carbon on a weight basis). Carbon materials include ultrapureas well as amorphous and crystalline carbon materials. Some carbonmaterials may comprise electrochemical modifiers (e.g. Si or N) tomodify (e.g., enhance) device performance as described in more detailbelow. Examples of carbon materials include, but are not limited to,activated carbon, pyrolyzed dried polymer gels, pyrolyzed polymercryogels, pyrolyzed polymer xerogels, pyrolyzed polymer aerogels,activated dried polymer gels, activated polymer cryogels, activatedpolymer xerogels, activated polymer aerogels and the like.

“Electrochemical modifier” refers to any chemical element, compoundcomprising a chemical element or any combination of different chemicalelements and compounds which modifies (e.g., enhances or decreases) theelectrochemical performance of a carbon material. Electrochemicalmodifiers can change (increase or decrease) the resistance, capacity,power performance, stability and other properties of a carbon material.Electrochemical modifiers generally impart a desired electrochemicaleffect. In contrast, an impurity in a carbon material is generallyundesired and tends to degrade, rather than enhance, the electrochemicalperformance of the carbon material. Examples of electrochemicalmodifiers within the context of the present disclosure include, but arenot limited to, elements, and compounds or oxides comprising elements,in groups 12-15 of the periodic table, other elements such as sulfur,tungsten and silver and combinations thereof. For example,electrochemical modifiers include, but are not limited to, lead, tin,antimony, bismuth, arsenic, tungsten, silver, zinc, cadmium, indium,silicon and combinations thereof as well as oxides of the same andcompounds comprising the same.

“Group 12” elements include zinc (Zn), cadmium (Cd), mercury (Hg), andcopernicium (Cn).

“Group 13” elements include boron (B), aluminum (Al), gallium (Ga),indium (In) and thallium (Tl).

“Group 14” elements include carbon (C), silicon (Si), germanium (Ge),tin (Sn) and lead (Pb).

“Group 15” elements include nitrogen (N), phosphorous (P), arsenic (As),antimony (Sb) and bismuth (Bi).

“Amorphous” refers to a material, for example an amorphous carbonmaterial, whose constituent atoms, molecules, or ions are arrangedrandomly without a regular repeating pattern. Amorphous materials mayhave some localized crystallinity (i.e., regularity) but lack long-rangeorder of the positions of the atoms. Pyrolyzed and/or activated carbonmaterials are generally amorphous.

“Crystalline” refers to a material whose constituent atoms, molecules,or ions are arranged in an orderly repeating pattern. Examples ofcrystalline carbon materials include, but are not limited to, diamondand graphene.

“Synthetic” refers to a substance which has been prepared by chemicalmeans rather than from a natural source. For example, a synthetic carbonmaterial is one which is synthesized from precursor materials and is notisolated from natural sources.

“Impurity” or “impurity element” refers to an undesired foreignsubstance (e.g., a chemical element) within a material which differsfrom the chemical composition of the base material. For example, animpurity in a carbon material refers to any element or combination ofelements, other than carbon, which is present in the carbon material.Impurity levels are typically expressed in parts per million (ppm).

“PIXE impurity” or “PIXE element” is any impurity element having anatomic number ranging from 11 to 92 (i.e., from sodium to uranium). Thephrases “total PIXE impurity content” and “total PIXE impurity level”both refer to the sum of all PIXE impurities present in a sample, forexample, a polymer gel or a carbon material. PIXE impurityconcentrations and identities may be determined by proton induced x-rayemission (PIXE).

“Ultrapure” refers to a substance having a total PIXE impurity contentof less than 0.050%. For example, an “ultrapure carbon material” is acarbon material having a total PIXE impurity content of less than 0.050%(i.e., 500 ppm).

“Ash content” refers to the nonvolatile inorganic matter which remainsafter subjecting a substance to a high decomposition temperature.Herein, the ash content of a carbon material is calculated from thetotal PIXE impurity content as measured by proton induced x-rayemission, assuming that nonvolatile elements are completely converted toexpected combustion products (i.e., oxides).

“Polymer” refers to a macromolecule comprised of one or more structuralrepeating units.

“Synthetic polymer precursor material” or “polymer precursor” refers tocompounds used in the preparation of a synthetic polymer. Polymerprecursors are generally compounds which may combined (i.e., reacted)with other compounds to form a polymer, for example a condensationpolymer. Polymer precursors include monomers, as well as monomers whichhave been partially polymerized (i.e., dimers, oligomers, etc.).Generally, the polymer precursors are selected from aromatic oraliphatic alcohols or amines and carbonyl containing compounds (e.g.,carboxylic acids, ketones, aledehydes, isocyanates, ureas, amides, acidhalides, esters, activated carbonyl-containing compounds and the like).Examples of polymer precursors that can be used in certain embodimentsof the preparations disclosed herein include, but are not limited to,aldehydes (i.e., HC(═O)R, where R is an organic group), such as forexample, methanal (formaldehyde); ethanal (acetaldehyde); propanal(propionaldehyde); butanal (butyraldehyde); glucose; benzaldehyde andcinnamaldehyde. Other exemplary polymer precursors include, but are notlimited to, phenolic compounds such as phenol and polyhydroxy benzenes,such as dihydroxy or trihydroxy benzenes, for example, resorcinol (i.e.,1,3-dihydroxy benzene), catechol, hydroquinone, and phloroglucinol.Amines, such as melamine, and urea may also be used. Mixtures of two ormore polyhydroxy benzenes are also contemplated within the meaning ofpolymer precursor.

“Condensation polymer” is a polymer that results from reaction of one ormore polymer precursors with elimination of a small molecule (e.g.water). Exemplary condensation polymers include, but are not limited to,polymers formed from reaction of an alcohol or amine with a carbonylcontaining compound.

“Monolithic” refers to a solid, three-dimensional structure that is notparticulate in nature.

“Sol” refers to a colloidal suspension of precursor particles (e.g.,polymer precursors), and the term “gel” refers to a wetthree-dimensional porous network obtained by condensation or reaction ofthe precursor particles.

“Polymer gel” refers to a gel in which the network component is apolymer; generally a polymer gel is a wet (aqueous or non-aqueous based)three-dimensional structure comprised of a polymer formed from syntheticprecursors or polymer precursors.

“Sol gel” refers to a sub-class of polymer gel where the polymer is acolloidal suspension that forms a wet three-dimensional porous networkobtained by reaction of the polymer precursors.

“Polymer hydrogel” or “hydrogel” refers to a subclass of polymer gel orgel wherein the solvent for the synthetic precursors or monomers iswater or mixtures of water and one or more water-miscible solvent.

“RF polymer hydrogel” refers to a sub-class of polymer gel wherein thepolymer was formed from the catalyzed reaction of resorcinol andformaldehyde in water or mixtures of water and one or morewater-miscible solvent.

“Continuous Phase” refers to the liquid phase in which thepolymerization components (i.e., polymer precursors, catalyst, acid,etc.) are dissolved, suspended and/or emulsified. Continuous phases maybe either hydrophilic or hydrophobic and have varying viscosities.Mixtures of two or more different continuous phases are alsocontemplated. Any number of different liquids (e.g., solvents) may beemployed within the context of the invention as described in more detailherein.

“Acid” refers to any substance that is capable of lowering the pH of asolution. Acids include Arrhenius, Brønsted and Lewis acids. A “solidacid” refers to a dried or granular compound that yields an acidicsolution when dissolved in a solvent. The term “acidic” means having theproperties of an acid.

“Base” refers to any substance that is capable of raising the pH of asolution. Bases include Arrhenius, Brønsted and Lewis bases. A “solidbase” refers to a dried or granular compound that yields basic solutionwhen dissolved in a solvent. The term “basic” means having theproperties of a base.

“Mixed solvent system” refers to a solvent system comprised of two ormore solvents, for example, two or more miscible solvents. Examples ofbinary solvent systems (i.e., a mixed solvent containing two solvents)include, but are not limited to: water and acetic acid; water and formicacid; water and propionic acid; water and butyric acid and the like.Examples of ternary solvent systems (i.e., containing three solvents)include, but are not limited to: water, acetic acid, and ethanol; water,acetic acid and acetone; water, acetic acid, and formic acid; water,acetic acid, and propionic acid; and the like. The present inventioncontemplates all mixed solvent systems comprising two or more solvents.

“Miscible” refers to the property of a mixture wherein the mixture formsa single phase over certain ranges of temperature, pressure, andcomposition.

“Catalyst” is a substance which alters the rate of a chemical reaction.Catalysts participate in a reaction in a cyclic fashion such that thecatalyst is cyclically regenerated. The present disclosure contemplatescatalysts which are sodium free. The catalyst used in the preparation ofa polymer gel (e.g., an ultrapure polymer gel) as described herein canbe any compound that facilitates the polymerization of the polymerprecursors to form an ultrapure polymer gel. A “volatile catalyst” is acatalyst which has a tendency to vaporize at or below atmosphericpressure. Exemplary volatile catalysts include, but are not limited to,ammoniums salts, such as ammonium bicarbonate, ammonium carbonate,ammonium hydroxide, and combinations thereof.

“Solvent” refers to a substance which dissolves or suspends reactants(e.g., ultrapure polymer precursors) and provides a medium in which areaction may occur. Examples of solvents useful in the preparation ofthe gels, ultrapure polymer gels, ultrapure synthetic carbon materialsand ultrapure synthetic amorphous carbon materials disclosed hereininclude, but are not limited to, water, alcohols and mixtures thereof.Exemplary alcohols include ethanol, t-butanol, methanol and mixturesthereof. Such solvents are useful for dissolution of the syntheticultrapure polymer precursor materials, for example dissolution of aphenolic or aldehyde compound. In addition, in some processes suchsolvents are employed for solvent exchange in a polymer hydrogel (priorto freezing and drying), wherein the solvent from the polymerization ofthe precursors, for example, resorcinol and formaldehyde, is exchangedfor a pure alcohol. In one embodiment of the present application, acryogel is prepared by a process that does not include solvent exchange.

“Dried gel” or “dried polymer gel” refers to a gel or polymer gel,respectively, from which the solvent, generally water, or mixture ofwater and one or more water-miscible solvents, has been substantiallyremoved.

“Pyrolyzed dried polymer gel” refers to a dried polymer gel which hasbeen pyrolyzed but not yet activated, while an “activated dried polymergel” refers to a dried polymer gel which has been activated.

“Cryogel” refers to a dried gel that has been dried by freeze drying.

“RF cryogel” refers to a dried gel that has been dried by freeze dryingwherein the gel was formed from the catalyzed reaction of resorcinol andformaldehyde.

“Pyrolyzed cryogel” is a cryogel that has been pyrolyzed but not yetactivated.

“Activated cryogel” is a cryogel which has been activated to obtainactivated carbon material.

“Xerogel” refers to a dried gel that has been dried by air drying, forexample, at or below atmospheric pressure.

“Pyrolyzed xerogel” is a xerogel that has been pyrolyzed but not yetactivated.

“Activated xerogel” is a xerogel which has been activated to obtainactivated carbon material.

“Aerogel” refers to a dried gel that has been dried by supercriticaldrying, for example, using supercritical carbon dioxide.

“Pyrolyzed aerogel” is an aerogel that has been pyrolyzed but not yetactivated.

“Activated aerogel” is an aerogel which has been activated to obtainactivated carbon material.

“Organic extraction solvent” refers to an organic solvent added to apolymer hydrogel after polymerization of the polymer precursors hasbegun, generally after polymerization of the polymer hydrogel iscomplete.

“Rapid multi-directional freezing” refers to the process of freezing apolymer gel by creating polymer gel particles from a monolithic polymergel, and subjecting said polymer gel particles to a suitably coldmedium. The cold medium can be, for example, liquid nitrogen, nitrogengas, or solid carbon dioxide. During rapid multi-directional freezingnucleation of ice dominates over ice crystal growth. The suitably coldmedium can be, for example, a gas, liquid, or solid with a temperaturebelow about −10° C. Alternatively, the suitably cold medium can be agas, liquid, or solid with a temperature below about −20° C.Alternatively, the suitably cold medium can be a gas, liquid, or solidwith a temperature below about −30° C.

“Activate” and “activation” each refer to the process of heating a rawmaterial or carbonized/pyrolyzed substance at an activation dwelltemperature during exposure to oxidizing atmospheres (e.g., carbondioxide, oxygen, steam or combinations thereof) to produce an“activated” substance (e.g., activated cryogel or activated carbonmaterial). The activation process generally results in a stripping awayof the surface of the particles, resulting in an increased surface area.Alternatively, activation can be accomplished by chemical means, forexample, by impregnation of carbon-containing precursor materials withchemicals such as acids like phosphoric acid or bases like potassiumhydroxide, sodium hydroxide or salts like zinc chloride, followed bycarbonization. “Activated” refers to a material or substance, forexample a carbon material, which has undergone the process ofactivation.

“Carbonizing”, “pyrolyzing”, “carbonization” and “pyrolysis” each referto the process of heating a carbon-containing substance at a pyrolysisdwell temperature in an inert atmosphere (e.g., argon, nitrogen orcombinations thereof) or in a vacuum such that the targeted materialcollected at the end of the process is primarily carbon. “Pyrolyzed”refers to a material or substance, for example a carbon material, whichhas undergone the process of pyrolysis.

“Dwell temperature” refers to the temperature of the furnace during theportion of a process which is reserved for maintaining a relativelyconstant temperature (i.e., neither increasing nor decreasing thetemperature). For example, the pyrolysis dwell temperature refers to therelatively constant temperature of the furnace during pyrolysis, and theactivation dwell temperature refers to the relatively constanttemperature of the furnace during activation.

“Pore” refers to an opening or depression in the surface, or a tunnel ina carbon material, such as for example activated carbon, pyrolyzed driedpolymer gels, pyrolyzed polymer cryogels, pyrolyzed polymer xerogels,pyrolyzed polymer aerogels, activated dried polymer gels, activatedpolymer cryogels, activated polymer xerogels, activated polymer aerogelsand the like. A pore can be a single tunnel or connected to othertunnels in a continuous network throughout the structure.

“Pore structure” refers to the layout of the surface of the internalpores within a carbon material, such as an activated carbon material.Components of the pore structure include pore size, pore volume, surfacearea, density, pore size distribution and pore length. Generally thepore structure of an activated carbon material comprises micropores andmesopores. For example, in certain embodiments the ratio of microporesto mesopores is optimized for enhanced electrochemical performance.

“Mesopore” generally refers to a pore having a diameter ranging from 2nanometers to 50 nanometers while the term “micropore” refers to a porehaving a diameter less than 2 nanometers.

“Surface area” refers to the total specific surface area of a substancemeasurable by the BET technique. Surface area is typically expressed inunits of m²/g. The BET (Brunauer/Emmett/Teller) technique employs aninert gas, for example nitrogen, to measure the amount of gas adsorbedon a material and is commonly used in the art to determine theaccessible surface area of materials.

“Connected” when used in reference to mesopores and micropores refers tothe spatial orientation of such pores.

“Effective length” refers to the portion of the length of the pore thatis of sufficient diameter such that it is available to accept salt ionsfrom the electrolyte.

“Electrode” refers to a conductor through which electricity enters orleaves an object, substance or region.

“Binder” refers to a material capable of holding individual particles ofa substance (e.g., a carbon material) together such that after mixing abinder and the particles together the resulting mixture can be formedinto sheets, pellets, disks or other shapes. In certain embodiments, anelectrode may comprise the disclosed carbon materials and a binder.Non-exclusive examples of binders include fluoro polymers, such as, forexample, PTFE (polytetrafluoroethylene, Teflon), PFA (perfluoroalkoxypolymer resin, also known as Teflon), FEP (fluorinated ethylenepropylene, also known as Teflon), ETFE (polyethylenetetrafluoroethylene,sold as Tefzel and Fluon), PVF (polyvinyl fluoride, sold as Tedlar),ECTFE (polyethylenechlorotrifluoroethylene, sold as Halar), PVDF(polyvinylidene fluoride, sold as Kynar), PCTFE(polychlorotrifluoroethylene, sold as Kel-F and CTFE), trifluoroethanoland combinations thereof.

“Inert” refers to a material that is not active in the electrolyte of anelectrical energy storage device, that is it does not absorb asignificant amount of ions or change chemically, e.g., degrade.

“Conductive” refers to the ability of a material to conduct electronsthrough transmission of loosely held valence electrons.

“Current collector” refers to a part of an electrical energy storageand/or distribution device which provides an electrical connection tofacilitate the flow of electricity in to, or out of, the device. Currentcollectors often comprise metal and/or other conductive materials andmay be used as a backing for electrodes to facilitate the flow ofelectricity to and from the electrode.

“Electrolyte” means a substance containing free ions such that thesubstance is electrically conductive. Electrolytes are commonly employedin electrical energy storage devices. Examples of electrolytes include,but are not limited to, solvents such as propylene carbonate, ethylenecarbonate, butylene carbonate, dimethyl carbonate, methyl ethylcarbonate, diethyl carbonate, sulfolane, methylsulfolane, acetonitrileor mixtures thereof in combination with solutes such astetralkylammonium salts such as TEA TFB (tetraethylammoniumtetrafluoroborate), MTEATFB (methyltriethylammonium tetrafluorob orate),EMITFB (1-ethyl-3-methylimidazolium tetrafluoroborate),tetraethylammonium, triethylammonium based salts or mixtures thereof. Insome embodiments, the electrolyte can be a water-based acid orwater-based base electrolyte such as mild aqueous sulfuric acid oraqueous potassium hydroxide.

“Amine” is a compound including a nitrogen atom, such as —NH2.

An “alcohol” is a compound including a —OH moiety.

A “carbonyl” is a compound including a carbon double bonded to oxygen(C═O).

A “phenol” refers to an aromatic ring (e.g., benzene) having one or morealcohol moieties attached thereto. Phenol and resorcinol are both“phenols.”

“Polyalcohol” refers to any compound having more than one alcoholmoiety.

“Sugar” is a polyalcohol such as glucose, fructose, lactose and thelike.

“Alkylamine” refers to an alkyl group (i.e., a saturated or unsaturatedoptionally substituted hydrocarbon compound) comprising an amine moiety(e.g., methyl amine and the like).

“Aromatic amine” refers to an aromatic group (i.e., a cyclic,unsaturated hydrocarbon having a cyclic array of conjugated pi bonds,such as benzene) comprising an amine group (e.g. aniline and the like).

An “aldehyde” is a compound comprising a —C(═O)H moiety.

“Ketone” refers to a compound comprising a —C(═O)— moiety.

A “carboxylic acid” is a compound containing a —C(═O)OH moiety.

“Esters” include compounds having a —C(═O)O— moiety.

An “acid halide” is any compound comprising a —C(═O)X moiety, wherein Xis fluorine, chlorine, bromine, iodide or astatine.

“Isocyanate” refers to compounds comprising a —N═C═O moiety.

“GM”, otherwise referred to as gerameter, is a measurement of therelative micro-, meso- and macro-porosity of a carbon sample. It iscalculated in the following fashion GM=[BET specific surface area(m2/g)]/[100*Pore Volume (cm3/g)] and units are generally not reported.Generally, microporous carbon exhibits a GM of greater than 21. Incertain embodiments, the microporous carbon exhibits a GM greater than22, greater than 23, greater than 24. Generally, carbons with micro- andmesoporous structure exhibits a GM between 9 and 21. In certainembodiments, carbons with micro- and mesoporous structure exhibits a GMbetween 9 and 15, between 11 and 15. Generally, carbons with micro- andmeso- and macroporous structure exhibit a Gm between 5 and 9. In certainembodiments, carbons with micro- and meso- and macoporous structureexhibits a GM between 7 and 7. In certain various other embodiments, thecarbon materials have a GM up to 25, up to 26, up to 28 up to 30 or evenup to 35.

As used herein, “normalized F/cc” or “maximum theoretical F/cc” isdefined as the capacitance expressed per envelope volume of carbonparticles (the sum of carbon skeletal volume and carbon pore volume);note that this envelope volume does not include any inter-particlevolume.

As used herein, “CMC” is the critical micelle concentration, defined asthe concentration above which surfactants form micelles, and alladditional surfactants added to the system go to micelles. In someembodiments, the surfactant level can be at a concentration above theCMC. In other embodiments, the surfactant level can be at aconcentration below the CMC. For example, the surfactant level can bepresent at a concentration less than 50% of the CMC, or less than 10% ofthe CMC, or less than 1% of the CMC, or less than 0.1% of the CMC, orless than 0.01% of the CMC.

“Carrier fluid” or “carrier phase” can refer to a suspension fluid,solvent, diluent, dispersion fluid, emulsion fluid, and/or thecontinuous phase of the suspension and/or emulsion. In one or moreembodiments, the term “continuous phase” has the same definition as“carrier fluid.” In one or more embodiments, the term carrier fluid hasthe same definition as “continuous phase.” In one or more embodiments,the term “carrier fluid” has the same definition as “solvent.” In one ormore embodiments, the term “solvent” has the same definition as “carrierfluid”.

As used herein, “particle size” refers to the volume average particlesize (Dv,50) as measured either by visual counting and measurement ofindividual particles or by laser light scattering of particles in asuspension fluid. The volume average particle size is determined byimage capture using a digital camera and ImageJ freeware, for particlesabove 0.1 mm in diameter. Particles sizes below 0.1 mm are determined bydilute dispersions in water by light scattering using a MalvernMASTERSIZER 3000. Samples below 0.1 mm are added to the Malvern analyzeruntil the recommended obscuration level is obtained.

“Suspension process,” “suspension polymerization process,” “dispersionprocess,” and “dispersion polymerization process” are usedinterchangeably and refer to a heterogeneous polymerization process thatmixes the reactant mixture in the “carrier phase” or “continuous phase”fluid such as a hydrocarbon and/or water, where the reactant mixturephase and the carrier or continuous phase fluid are not miscible. Insome embodiments, the reactant mixture can be suspended or dispersed inthe carrier fluid or continuous phase as droplets, where the monomercomponent undergoes polymerization to form particles of polymer and/orcuring to form cured particles of polymer. In some embodiments, thereaction mixture can be agitated. In some embodiments, the reactionmixture is not agitated.

“Emulsion process” and “emulsion polymerization process” refer to both“normal” emulsions and “inverse” emulsions. Emulsions differ fromsuspensions in one or more aspects. One difference is that an emulsionwill usually include the use of a surfactant that creates or forms theemulsions (very small size droplets). When the carrier or continuousphase fluid is a hydrophilic fluid such as water and the reactantmixture phase is a hydrophobic compound(s), normal emulsions (e.g.,oil-in-water) form, where droplets of monomers are emulsified with theaid of a surfactant in the carrier or continuous phase fluid. Monomersreact in these small size droplets. These droplets are typically smallin size as the particles are stopped from coagulating with each otherbecause each particle is surrounded by the surfactant and the charge onthe surfactant electrostatically repels other particles. Whereassuspension polymerization usually creates much larger particles thanthose made with emulsion polymerization. When the carrier or continuousphase fluid is a hydrophobic fluid such as oil and the reactant mixturephase is hydrophilic compounds, inverse-emulsions (e.g., water-in-oil)form.

As used herein, the terms “suspension and/or emulsion process” and“suspension and/or emulsion polymerization” are not limited to ornecessarily refer to traditional polymerization. Instead, the terms“suspension and/or emulsion process” and “suspension and/or emulsionpolymerization” may, but not necessarily, refer to a curing process or acombination of traditional polymerization and a curing process. Asdiscussed and described herein, in one or more embodiments, the monomercomponent can be or include a pre-polymer and/or a polymer in additionto or in lieu of the monomer mixture alone. The curing process refers tothe further cross-linking or hardening of the polymer as compared to thepolymerization of a monomer mixture. As such, if a pre-polymer ispresent, the suspension/emulsion process can, in addition to or in lieuof polymerization, also include the curing process. As used herein, theterm “curing” refers to the toughening or hardening of polymers via anincreased degree of cross-linking of polymer chains. Cross-linkingrefers to the structural and/or morphological change that occurs in thepre-polymer and/or polymer, such as by covalent chemical reaction, ionicinteraction or clustering, phase transformation or inversion, and/orhydrogen bonding.

As used herein, the terms “polymer particulates in gel form” and“polymer particles in gel form” are used interchangeably and refer to anetwork of polymer chains that have one or more pores or voids therein,and a liquid at least partially occupies or fills the one or more poresor voids. As used herein, the terms “dried polymer particulates” and“dried polymer particles” are used interchangeably and refer to anetwork of polymer chains having one or more pores or voids therein, anda gas at least partially occupies or fills the one or more pores orvoids. If the liquid that at least partially occupies or fills the voidsis water, the polymer particles can be referred to as “hydrogel polymerparticles.”

“Monomer component” can include, but is not limited to, one or morephenolic compounds and/or one or more crosslinking compounds and/or aprepolymer formed by pre-polymerizing the one or more phenolic compoundsand/or the one more crosslinking compounds. If the phenolic compound canpolymerize and crosslink with itself, the use of the crosslinkingcompound can be optional. In another example, the phenolic compound andall or a portion of the crosslinking compound can polymerize with oneanother to form the polymer particles in gel form. In another example,the phenolic compound and the crosslinking compound can react orcrosslink with one another to produce the polymer particles in gel form.In another example, the phenolic compound and the crosslinking compoundcan polymerize with one another and/or crosslink with one another toproduce the polymer particles in gel form.

In one or more embodiments, the terms “monomer component” and “polymerphase” are equivalent. In one or more embodiments, the terms “monomercomponent” and “polymer precursor” are equivalent.

As used herein, the term “prepolymer” refers to the reacted monomercompounds of the one or more phenolic compounds and the one or morecrosslinking compounds; and/or a polymer formed by polymerizing the oneor more phenolic compounds and/or the one more crosslinking compounds solong as the polymer remains in liquid form.

A. Preparation of Polymer Gels and Carbon Materials

The disclosed preparation of carbon materials represents a number ofadvances over currently known methods for preparation of carbonmaterials. For example, similar carbon materials have traditionally beenmade by admixing polymer precursors and allowing them to polymerize intoa polymer monolith. The monolith must then be isolated and ground ormilled to small particles before it can be pyrolyzed and/or activatedinto carbon materials. Such procedures suffer from a number ofdrawbacks. For example, at large scales previously described monolithpreparations present significant material handling problems and thepossibility of heterogenous polymerizations and/or uncontrolledexothermic reactions. Furthermore, other considerations, such as theincompatibility of typical production equipment (e.g., ovens, etc.) withknown monolith procedures, makes scale up of these procedureschallenging and economically difficult.

The present methods overcome these limitations and represent a number ofother improvements. For example, the described polymerizations providethe possibility to isolate the gel product by filtration or by decantingexcess solvent, thus making the methods amendable to large scaleproduction. Furthermore, heat transfer is more effective in the presentmethods compared to monolith procedures, thus the products are expectedto be more homogeneous and the risk of uncontrolled exotherms issignificantly reduced. Furthermore, by changing the gel formulationand/or processing parameters, carbon materials having certain desiredcharacteristics (e.g., microporosity, mesoporosity, high density, lowdensity, specific particle sizes, near monodisperse particle sizedistributions, etc.) can be obtained without additional processing steps(e.g., milling, etc.). Certain aspects of the disclosed methods aredescribed in more detail in the following sections.

The various physical and chemical properties of the carbon materials andpolymer gels are as described in the following section and as disclosedin co-pending U.S. application Ser. Nos. 12/748,219; 12/897,969;12/829,282; 13/046,572; 12/965,709; 13/336,975; and 61/585,611, each ofwhich are hereby incorporated by reference in their entireties for allpurposes.

1. Preparation of Polymer Gels

As noted above, on embodiment of the present disclosure provides methodsfor preparation of polymer gels and carbon materials. For example, inone embodiment the present disclosure provides a method for makingpolymer particles in gel form via an emulsion or suspension process, themethod comprising:

a) preparing a reactant mixture comprising a monomer componentcomprising one or more phenolic compounds, one or more crosslinkingcompounds, and a carrier fluid; and

b) polymerizing the one or more phenolic compounds with the one or morecrosslinking compounds,

wherein the carrier fluid comprises a surfactant in a concentrationequal to or greater than the critical micelle concentration and thevolume average particle size (Dv,50) of the polymer particles is lessthan or equal to 1 mm.

In another embodiment, the disclosure provides a method for makingpolymer particles in gel form via an emulsion or suspension process, themethod comprising:

a) preparing a reactant mixture comprising a monomer componentcomprising one or more phenolic compounds, one or more crosslinkingcompounds, and a carrier fluid; and

b) polymerizing the one or more phenolic compounds with the one or morecrosslinking compounds,

wherein the carrier fluid comprises 50 wt % or more of cyclohexane,based on the total weight of the carrier fluid, and the volume averageparticle size (Dv,50) of the polymer particles is less than or equal to1 mm.

In still other embodiments, the disclosure is directed to a method formaking polymer particles in gel form via an emulsion or suspensionprocess, the method comprising:

a) preparing a reactant mixture comprising a monomer componentcomprising one or more phenolic compounds, one or more crosslinkingcompounds, and a carrier fluid; and

b) polymerizing the one or more phenolic compounds with the one or morecrosslinking compounds,

wherein the carrier fluid comprises 50 wt % or more of cyclohexane,based on the total weight of the carrier fluid, and the volume averageparticle size (Dv,50) of the polymer particles is greater than or equalto 1 mm.

In another embodiment the present application provides a method forpreparing a condensation polymer gel via an emulsion or suspensionprocess, the method comprising:

a) preparing a mixture comprising a continuous phase and a polymerphase, wherein the polymer phase comprises one or more polymerprecursors and an optional solvent; and

b) aging the mixture at a temperature and for a time sufficient for theone or more polymer precursors to react with each other and form acondensation polymer gel.

In another embodiment, the disclosed methods include preparing a driedcondensation polymer gel, the method comprises drying a condensationpolymer gel, wherein the condensation polymer gel has been prepared byan emulsion or suspension process comprising:

a) preparing a mixture comprising a continuous phase and a polymerphase, wherein the polymer phase comprises one or more polymerprecursors and an optional solvent; and

b) aging the mixture at a temperature and for a time sufficient for theone or more polymer precursors to react with each other and form acondensation polymer gel.

In yet other embodiments, the invention provides a method for preparinga carbon material, the method comprising heating condensation polymergel particles to obtain a carbon material, wherein the condensationpolymer gel particles have been prepared by a process comprising:

a) preparing a mixture comprising a continuous phase and a polymerphase, wherein the polymer phase comprises one or more polymerprecursors and an optional solvent; and

b) aging the mixture at a temperature and for a time sufficient for theone or more polymer precursors to react with each other and form acondensation polymer gel.

The condensation polymer gel may be used without drying or the methodsmay further comprise drying the condensation polymer gel. In certainembodiments of the foregoing methods, the polymer gel is dried by freezedrying.

The inventive methods are useful for preparation of condensation polymergels and/or carbon materials having any number of various porestructures. In this regard, Applications have discovered that the porestructure can be controlled by variation of any number of processparameters such as continuous phase type, stir rate, temperature, agingtime, etc. In some embodiments, the condensation polymer gel ismicroporous, and in other embodiments the condensation polymer gel ismesoporous. In certain other embodiments, the condensation polymer gelcomprises a pore structure having a mixture of microporous andmesoporous pores.

In related embodiments, the carbon material is microporous or the carbonmaterial is mesoporous. In other embodiments, the carbon materialcomprises a pore structure having mixture of microporous and mesoporouspores.

The polymer phase may be prepared by admixing the one or more polymerprecursors and the optional solvent, and in some examples the mixture isprepared by admixing the continuous phase and the polymer phase. Themethod includes embodiments wherein the mixture is an emulsion, while inother embodiments the mixture is a suspension.

For example, in some embodiments the continuous phase and the polymerphase are not miscible with each other, and the mixture is an emulsion.While in other exemplary methods the continuous phase and the polymerphase are not soluble in each other, and the mixture is a suspension. Inother examples, the polymer phase is aged prior to preparation of themixture, and the mixture is an emulsion and/or a suspension uponcombination of the continuous phase and the polymer phase.

In other different aspects, both the continuous phase and the polymerphase are soluble in each other (i.e., miscible). In some variations ofthis embodiment, the continuous phase and polymer phase are miscibleinitially but the polymer phase is aged such that it becomes immisciblewith the continuous phase and the mixture becomes a suspension uponaging.

The polymer phase may be prepared by admixing the one or more polymerprecursors and the optional solvent. In some embodiments, the polymerphase is “pre-reacted” prior to mixing with the continuous phase suchthe polymer precursors are at least partially polymerized. In otherembodiments, the polymer precursors are not pre-reacted. In certainother embodiments, the method is a continuous process. For example, thepolymer precursors may be continuously mixed with a continuous phase andthe final condensation polymer gel may be continuously isolated from themixture.

A single polymer precursor may be used or the methods may comprise useof two or more different polymer precursors. The structure of thepolymer precursors is not particularly limited, provided that thepolymer precursor is capable of reacting with another polymer precursoror with a second polymer precursor to form a polymer. Polymer precursorsinclude amine-containing compounds, alcohol-containing compounds andcarbonyl-containing compounds, for example in some embodiments thepolymer precursors are selected from an alcohol, a phenol, apolyalcohol, a sugar, an alkyl amine, an aromatic amine, an aldehyde, aketone, a carboxylic acid, an ester, a urea, an acid halide and anisocyanate.

In one embodiment, the method comprises use of a first and secondpolymer precursor, and in some embodiments the first or second polymerprecursor is a carbonyl containing compound and the other of the firstor second polymer precursor is an alcohol containing compound. In someembodiments, a first polymer precursor is a phenolic compound and asecond polymer precursor is an aldehyde compound (e.g., formaldehyde).In one embodiment, of the method the phenolic compound is phenol,resorcinol, catechol, hydroquinone, phloroglucinol, or a combinationthereof; and the aldehyde compound is formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, benzaldehyde, cinnamaldehyde, or acombination thereof. In a further embodiment, the phenolic compound isresorcinol, phenol or a combination thereof, and the aldehyde compoundis formaldehyde. In yet further embodiments, the phenolic compound isresorcinol and the aldehyde compound is formaldehyde. In someembodiments, the polymer precursors are alcohols and carbonyl compounds(e.g., resorcinol and aldehyde) and they are present in a ratio of about0.5:1.0, respectively.

The polymer precursor materials as disclosed herein include (a)alcohols, phenolic compounds, and other mono- or polyhydroxy compoundsand (b) aldehydes, ketones, and combinations thereof. Representativealcohols in this context include straight chain and branched, saturatedand unsaturated alcohols. Suitable phenolic compounds includepolyhydroxy benzene, such as a dihydroxy or trihydroxy benzene.Representative polyhydroxy benzenes include resorcinol (i.e.,1,3-dihydroxy benzene), catechol, hydroquinone, and phloroglucinol.Mixtures of two or more polyhydroxy benzenes can also be used. Phenol(monohydroxy benzene) can also be used. Representative polyhydroxycompounds include sugars, such as glucose, sucrose, chitin and otherpolyols, such as mannitol. Aldehydes in this context include: straightchain saturated aldeydes such as methanal (formaldehyde), ethanal(acetaldehyde), propanal (propionaldehyde), butanal (butyraldehyde), andthe like; straight chain unsaturated aldehydes such as ethenone andother ketenes, 2-propenal (acrylaldehyde), 2-butenal (crotonaldehyde), 3butenal, and the like; branched saturated and unsaturated aldehydes; andaromatic-type aldehydes such as benzaldehyde, salicylaldehyde,hydrocinnamaldehyde, and the like. Suitable ketones include: straightchain saturated ketones such as propanone and 2 butanone, and the like;straight chain unsaturated ketones such as propenone, 2 butenone, and3-butenone (methyl vinyl ketone) and the like; branched saturated andunsaturated ketones; and aromatic-type ketones such as methyl benzylketone (phenylacetone), ethyl benzyl ketone, and the like. The polymerprecursor materials can also be combinations of the precursors describedabove.

In some embodiments, one polymer precursor is an alcohol-containingspecies and another polymer precursor is a carbonyl-containing species,for example an aldehyde and a phenol. The relative amounts ofalcohol-containing species (e.g., alcohols, phenolic compounds and mono-or poly-hydroxy compounds or combinations thereof) reacted with thecarbonyl containing species (e.g. aldehydes, ketones or combinationsthereof) can vary substantially. In some embodiments, the ratio ofalcohol-containing species to aldehyde species is selected so that thetotal moles of reactive alcohol groups in the alcohol-containing speciesis approximately the same as the total moles of reactive carbonyl groupsin the aldehyde species. Similarly, the ratio of alcohol-containingspecies to ketone species may be selected so that the total moles ofreactive alcohol groups in the alcohol containing species isapproximately the same as the total moles of reactive carbonyl groups inthe ketone species. The same general 1:1 molar ratio holds true when thecarbonyl-containing species comprises a combination of an aldehydespecies and a ketone species.

In certain embodiments, the polymer precursors comprise formaldehyde andresorcinol or formaldehyde and phenol. In other embodiments, the polymerprecursors comprise formaldehyde and urea.

In other embodiments, the polymer precursor is a urea or an aminecontaining compound. For example, in some embodiments the polymerprecursor is urea or melamine. Other embodiments include polymerprecursors selected from isocyanates or other activated carbonylcompounds such as acid halides and the like.

Some embodiments of the disclosed methods include preparation of polymergels (and carbon materials) comprising electrochemical modifiers.Electrochemical modifiers include those known in the art and describedin co-pending U.S. application Ser. No. 12/965,709, previouslyincorporated by reference in its entirety. Such electrochemicalmodifiers are generally selected from elements useful for modifying theelectrochemical properties of the resulting carbon materials or polymergels, and in some embodiments include nitrogen or silicon. In otherembodiments, the electrochemical modifier comprises nitrogen, iron, tin,silicon, nickel, aluminum or manganese. The electrochemical modifier canbe included in the preparation procedure at any step. For example, insome the electrochemical modifier is admixed with the mixture, thepolymer phase or the continuous phase.

The total solids content in the gel formulation prior to polymerformation can be varied. The weight ratio of resorcinol to water is fromabout 0.05 to 1 to about 0.70 to 1. Alternatively, the ratio ofresorcinol to water is from about 0.15 to 1 to about 0.6 to 1.Alternatively, the ratio of resorcinol to water is from about 0.15 to 1to about 0.35 to 1. Alternatively, the ratio of resorcinol to water isfrom about 0.25 to 1 to about 0.5 to 1. Alternatively, the ratio ofresorcinol to water is from about 0.3 to 1 to about 0.6 to 1.

In some embodiments, the gel polymerization process is performed undercatalytic conditions. Accordingly, in some embodiments, the methodcomprises admixing a catalyst with the mixture, the polymer phase and/orthe continuous phase. In some embodiments, the catalyst comprises abasic volatile catalyst. For example, in one embodiment, the basicvolatile catalyst comprises ammonium carbonate, ammonium bicarbonate,ammonium acetate, ammonium hydroxide, or combinations thereof. In afurther embodiment, the basic volatile catalyst is ammonium carbonate.In another further embodiment, the basic volatile catalyst is ammoniumacetate.

The molar ratio of catalyst to polymer precursor (e.g., phenoliccompound) may have an effect on the final properties of the polymer gelas well as the final properties of the carbon materials. Thus, in someembodiments such catalysts are used in the range of molar ratios of 5:1to 2000:1 polymer precursor:catalyst. In some embodiments, suchcatalysts can be used in the range of molar ratios of 10:1 to 400:1polymer precursor:catalyst. For example in other embodiments, suchcatalysts can be used in the range of molar ratios of 5:1 to 100:1polymer precursor:catalyst. For example, in some embodiments the molarratio of catalyst to polymer precursor is about 400:1. In otherembodiments the molar ratio of catalyst to polymer precursor is about100:1. In other embodiments the molar ratio of catalyst to polymerprecursor is about 50:1. In other embodiments the molar ratio ofcatalyst to polymer precursor is about 10:1. In certain of the foregoingembodiments, the polymer precursor is a phenolic compound such asresorcinol or phenol.

In the specific embodiment wherein one of the polymer precursors isresorcinol and another polymer precursor is formaldehyde, the resorcinolto catalyst ratio can be varied to obtain the desired properties of theresultant polymer gel and carbon materials. In some embodiments of themethods described herein, the molar ratio of resorcinol to catalyst isfrom about 5:1 to about 2000:1 or the molar ratio of resorcinol tocatalyst is from about 10:1 to about 400:1. In further embodiments, themolar ratio of resorcinol to catalyst is from about 5:1 to about 100:1.In further embodiments, the molar ratio of resorcinol to catalyst isfrom about 25:1 to about 50:1. In further embodiments, the molar ratioof resorcinol to catalyst is from about 100:1 to about 5:1.

In still other embodiments, the method comprises admixing an acid withthe mixture, the polymer phase and/or the continuous phase. The acid maybe selected from any number of acids suitable for the polymerizationprocess. For example, in some embodiments the acid is acetic acid and inother embodiments the acid is oxalic acid. In further embodiments, theacid is mixed with the first or second solvent in a ratio of acid tosolvent of 99:1, 90:10, 75:25, 50:50, 25:75, 20:80, 10:90 or 1:90. Inother embodiments, the acid is acetic acid and the first or secondsolvent is water. In other embodiments, acidity is provided by adding asolid acid to the emulsion, suspension or gel formulation.

The total content of acid in the mixture can be varied to alter theproperties of the final product. In some embodiments, the acid ispresent from about 1% to about 50% by weight of polymer solution. Inother embodiments, the acid is present from about 5% to about 25%. Inother embodiments, the acid is present from about 10% to about 20%, forexample about 10%, about 15% or about 20%.

Although a surfactant is not required (and is not present in certainembodiments), some embodiments include use of a surfactant. Thesurfactant may be admixed with the mixture, the polymer phase and/or thecontinuous phase or included in the process in any other appropriatemanner. In some embodiments which include a surfactant, the polymerphase is pre-reacted prior to mixing with the continuous phase such thepolymer precursors are at least partially polymerized.

The surfactant may be selected from any number of surfactants which areuseful for emulsifying two immiscible solutions. For example, in someembodiments the surfactant comprises a sorbitan surfactant such as SPAN™80, SPAN™ 85, SPAN™ 65, SPAN™ 60, SPAN™ 40, SPAN™ 20, TWEEN® 80, TWEEN®40, TWEEN® 20, TWEEN® 21, TWEEN® 60, TritonX® 100 or combinationsthereof. In certain embodiments, the surfactant comprises SPAN™ 80. Inother embodiments, the surfactant comprises SPAN™ 20.

Such surfactants are well known in the art and are availablecommercially from a number of sources, including Sigma-Aldrich, St.Louis Mo. While not wishing to be bound by theory, it is believed thatthe amount of surfactant present in the mixture may be a parameter thatcan be modified to control the physical properties of the resulting geland/or carbon materials. For example, surfactant concentrations lessthan or equal to about 2% may be associated with mesoporous carbons,while higher surfactant concentrations may be associated withmicroporous carbons. However, high concentrations of surfactant (e.g.,greater than about 30%) are not as effective. While surfactant may bedesirable in some embodiments, it is not required in all embodiments ofthe disclosed methods.

In some embodiments when surfactant is present, the mixture comprisesfrom about 0.01% to about 20% surfactant (w/w), for example about 0.1%to about 20% surfactant (w/w), for example about 10% surfactant. Inother embodiments, the mixture comprises from about 0.1% to about 10%surfactant, for example about 5% surfactant. In other embodiments, themixture comprises from about 0.1% to about 2% surfactant, for exampleabout 0.5% or about 1% surfactant. In other embodiments, the mixturecomprises from about 0.01% to about 1.0% surfactant, for example about0.1% to about 1.0% surfactant. In other embodiments, the mixturecomprises from about 1.0% to about 2.0% surfactant. In otherembodiments, the mixture comprises from about 2.0% to about 5.0%surfactant. In other embodiments, the mixture comprises from about 5.0%to about 10% surfactant. In some certain embodiments, the mixturecomprises about 0.1%, about 0.2%, about 0.3%, about 0.4%, about 0.5%,about 0.6%, about 0.7%, about 0.8%, about 0.9%, about 1.0%, about 1.1%,about 1.2%, about 1.3%, about 1.4%, about 1.5%, about 1.6%, about 1.7%,about 1.8%, about 1.9% or about 2.0% surfactant. In other embodiments,the emulsions, suspension or combination thereof comprise from about9.0% to about 11.0%, from about 0.05% to about 1.1% surfactant or fromabout 0.9% to about 1.1% surfactant.

The continuous phase is another process parameter that may be varied toobtain the desired properties (e.g., surface area, porosity, purity,etc.) of the polymer gels and carbon materials. For example, the presentinventors have surprisingly discovered that by careful selection of thecontinuous phase, the porosity of the final polymer gel and carbonmaterials can be controlled (see data provided in Examples). Thus, thepresent methods provide the ability to prepare carbon materials (and theprecursor gels) having any desired porosity. A further advantage ofcareful selection of the continuous phase is in the scaleability of theprocess. For example, when continuous phases are selected which have lowtoxicity, flammability, etc., the process is more amenable to scale upthan other known polymer processes.

In some embodiments of the method, the polymer phase and the continuousphase are not miscible with each other and an emulsion or suspension isformed. In other embodiments the polymer phase and continuous phase aremiscible or partially miscible with each other. In these cases thepolymer phase may become less miscible with the continuous phase overthe course of the reaction. In this respect, certain embodiments aredirected to methods wherein the optional solvent is an aqueous and/orpolar solvent and the continuous phase is an organic and/or nonpolarsolvent. Suitable aqueous and/or polar solvents include, but are notlimited to, water, water/acetic acid, alcohols (e.g., ethanol, methanol,etc.), polar ethers (e.g., PEG, etc.), organic acids (e.g., acetic) andmixtures thereof. In certain embodiments, the optional solvent ispresent. In certain embodiments, the optional solvent is present andcomprises water. For example, in some embodiments, the polymer phasecomprises water or an acetic acid/water mix.

Suitable organic and/or nonpolar solvents for use as a continuous phaseinclude hydrocarbon solvents, aromatic solvents, oils, nonpolar ethers,ketones and the like. For example, suitable organic and/or nonpolarsolvents include, but are not limited to hexane, cyclohexane, pentane,cyclopentane, benzene, toluene, xylenes, diethyl ether,ethylmethylketone, dichloromethane, tetrahydorfuran, mineral oils,paraffin oils, isopariffic fluids and the like. In some embodiments, thecontinuous phase is an organic solvent, for example a hydrocarbonsolvent. In more specific embodiments, the continuous phase iscyclohexane, mineral oil, paraffinic oil, xylene, isoparaffinic oils orcombinations thereof. In other embodiments, the continuous phase iscyclohexane, paraffinic oil, xylene, isoparaffinic oil or combinationsthereof. In some specific embodiments, the continuous phase comprisesparaffinic oil. In other specific embodiments, the optional solvent ispresent and comprises water and the continuous phase comprisescyclohexane, mineral oil, xylene or combinations thereof. In certainembodiments, the viscosity of the continuous phase is selected such thatcertain properties (e.g., particle size) of the polymer gel arecontrolled.

The wt % of organic and/or nonpolar solvent present in the continuousphase (carrier phase) can be varied depending on the particularapplication. For example, in certain embodiments the wt % of organicand/or nonpolar solvent in the carrier phase (based on total weight ofcarrier phase) is greater than 90%, greater than 80%, greater than 70%,greater than 60%, greater than 50%, greater than 40%, greater than 30%,greater than 20%, greater than 10%, greater than 5% or greater than 1%.In certain of the foregoing embodiments the organic and/or non polarsolvent is cyclohexane.

In some embodiments the continuous phase is selected to be amenable forlarge scale production. In this regard, continuous phase propertiesimportant for large scale production include low toxicity, lowflammability, price and/or ease of removal from final product and thelike. The continuous phase may also be selected to have high purity,which in turn may contribute to high purity of the final polymer geland/or carbon material. In this regard, continuous phases havingpurities greater than 99%, greater than 99.5%, greater than 99.9%,greater than 99.99% or even greater than 99.999% may be used.

In certain embodiments, the polymer precursor components are mixedtogether in a single aqueous phase and subsequently emulsified orsuspended with an outer non-aqueous phase using techniques known in theart, and subsequently held for a time and at a temperature sufficient toat a temperature sufficient to achieve complete polymerization ofprecursors within the aqueous phase. In other embodiments, the precursorcomponents are mixed together in a single aqueous phase, held for a timeand at a temperature sufficient to achieve partial polymerization, andsubsequently suspended in an outer non-aqueous phase using techniquesknown in the art, and subsequently held for a time and achieve completepolymerization of precursors within the aqueous phase. In thisembodiment, the partial polymerization step may result in increasedviscosity, allowing for control of polymer resin particle size dependingon the emulsification energy conditions and viscosities of the partiallypolymerized aqueous phase and the non-aqueous phase. In otherembodiments, the precursor components are mixed together in a singleaqueous phase, held for a time and at a temperature sufficient toachieve partial polymerization, and subsequently suspended in an outeraqueous phase using techniques known in the art, and subsequently heldfor a time and achieve complete polymerization of precursors within theaqueous phase. In this embodiment, the partial polymerization step mayresult in increased viscosity, allowing for control of polymer resinparticle size depending on the emulsification energy conditions,viscosities and immiscibility of the partially polymerized aqueous phaseand the continuous aqueous phase.

Reaction parameters include aging the mixture at a temperature and for atime sufficient for the one or more polymer precursors to react witheach other and form a polymer. In this respect, suitable agingtemperature ranges from about room temperature to temperatures at ornear the boiling point of the continuous phase. For example, in someembodiments the emulsion, suspension or combination thereof is aged attemperatures from about 20° C. to about 120° C., for example about 20°C. to about 100° C. Other embodiments include temperature ranging fromabout 30° C. to about 90° C., for example about 45° C. or about 85° C.In other embodiments, the temperature ranges from about 65° C. to about80° C., while other embodiments include aging at two or moretemperatures, for example about 45° C. and about 70-85° C. or about80-85° C. Aging may include stirring in certain embodiments.

The reaction duration is generally sufficient to allow the polymerprecursors to react and form a polymer, for example the mixture may beaged anywhere from 1 hour to 48 hours, or more or less depending on thedesired result. Typical embodiments include aging for a period of timeranging from about 2 hours to about 48 hours, for example in someembodiments aging comprises about 12 hours and in other embodimentsaging comprises about 4-8 hours (e.g., about 6 hours). Aging conditionsmay optionally include stirring, shaking or other means of agitating themixture. While not wishing to be bound by theory, it is thought thatstirring is a parameter that may be controlled to produce gels and/orcarbon materials having a desired particle size distribution (e.g., nearmondisperse, etc.). For example, the stirring RPMs may be adjusted toobtain the desired result. Such methods have the added advantage that anadditional step of milling or grinding to obtain the desired particlesize may not be needed.

Generally, the methods further comprise isolating the polymer gelparticles and/or carbon materials. Suitable means for isolating includefiltering, decanting a solvent or continuous phase or combinationsthereof. The isolated product may be further processed by methodsincluding drying the isolated polymer gel particles to remove volatilecontent, for example, freeze drying.

In some embodiments, the particle size distribution of the polymerparticles exhibit a polydispersity index (Dv,90−Dv,10)/Dv,50, whereinDv,10, Dv,50 and Dv,90 are the particle size at 10%, 50% and 90%,respectively of the particle size distribution by volume) less than1,000, for example less than 100, for example less than 10, for exampleless than 5, for example less than 3, for example less than 2, forexample less than 1.5, for example less than 1. In some embodiments,introduction of aqueous phase to organic phase can be staged such thattwo or more populations of polymer particle size distribution may beachieved. For example, the final polymer particle distribution achievedmay consist of two or more modes, where the ratio between the highestand lowest node is about 1000 or lower, for example about 100 or lower,for example about 50 or lower, for example about 10 or lower, forexample about 5 or lower, for example about 2 or lower.

Furthermore, the methods may comprise freeze drying the polymer gelparticles prior to pyrolyzing and/or activating, however such drying isnot required and the polymer gel can be pyrolyzed without drying. Insome embodiments, the polymer gel particles are frozen via immersion ina medium having a temperature of below about −10° C., for example, belowabout −20° C., or alternatively below about −30° C. For example, themedium may be liquid nitrogen or ethanol (or other organic solvent) indry ice or ethanol cooled by another means. In some embodiments, freezedrying comprises subjecting the frozen particles to a vacuum pressure ofbelow about 3000 mTorr. Alternatively, drying under vacuum comprisessubjecting the frozen particles to a vacuum pressure of below about 1000mTorr. Alternatively, drying under vacuum comprises subjecting thefrozen particles to a vacuum pressure of below about 300 mTorr.Alternatively, drying under vacuum comprises subjecting the frozenparticles to a vacuum pressure of below about 100 mTorr.

Other methods of rapidly freezing the polymer gel particles are alsoenvisioned. For example, in another embodiment the polymer gel israpidly frozen by co-mingling or physical mixing of polymer gelparticles with a suitable cold solid, for example, dry ice (solid carbondioxide). Another envisioned method comprises using a blast freezer witha metal plate at −60° C. to rapidly remove heat from the polymer gelparticles scattered over its surface. Another method of rapidly coolingwater in a polymer gel particle is to snap freeze the particle bypulling a high vacuum very rapidly (the degree of vacuum is such thatthe temperature corresponding to the equilibrium vapor pressure allowsfor freezing). Yet another method for rapid freezing comprises admixinga polymer gel with a suitably cold gas. In some embodiments the cold gasmay have a temperature below about −10° C. In some embodiments the coldgas may have a temperature below about −20° C. In some embodiments thecold gas may have a temperature below about −30° C. In yet otherembodiments, the gas may have a temperature of about −196° C. Forexample, in some embodiments, the gas is nitrogen. In yet otherembodiments, the gas may have a temperature of about −78° C. Forexample, in some embodiments, the gas is carbon dioxide.

In other embodiments, the polymer gel particles are frozen on alyophilizer shelf at a temperature of −20° C. or lower. For example, insome embodiments the polymer gel particles are frozen on the lyophilizershelf at a temperature of −30° C. or lower. In some other embodiments,the polymer gel monolith is subjected to a freeze thaw cycle (from roomtemperature to −20° C. or lower and back to room temperature), physicaldisruption of the freeze-thawed gel to create particles, and thenfurther lyophilization processing. For example, in some embodiments, thepolymer gel monolith is subjected to a freeze thaw cycle (from roomtemperature to −30° C. or lower and back to room temperature), physicaldisruption of the freeze-thawed gel to create particles, and thenfurther lyophilization processing.

The disclosed methods are useful for preparation of a wide variety ofcarbon materials. In one example, carbon materials having high densityand microporosity are prepared. Gel formulations useful in this regardinclude formulations comprising from 30-60% solids, 5%-30% acetic acid,5-50 R:C, 0.5-15% surfactant, and ≥20% RF solution, for example about46-50% solids, about 10% acetic acid, about 10 R:C, about 10%surfactant, and about ≥30% RF solution.

Mesoporous carbon materials can also be prepared by the disclosedmethods. Formulations useful in this regard include, but are not limitedto, from 25%-50% solids, 10-25% acetic acid, 50 to 400 R:C, 0.1-15%surfactant, and 15-35% RF solution, for example about 33% solids, about20% acetic acid, either 100 or 400 R:C, about 10% surfactant, and about20% RF solution. Other formulations useful for preparation of mesoporouscarbons include, but are not limited to, a formulation comprised of from25%-40% solids, 5%-15%% acid, 25-75 R:C, 0.5%-1.5% surfactant, and15%-25% RF, for example about 33% solids, about 10% acid, about 50 R:C,about 1% surfactant and about 20% RF solution.

As used herein, % solids is calculated as the mass of polymer precursors(excluding water) divided by the total mass of polymer precursors(including water), additional water and acid. Catalyst is not includedin the calculation of % solids. Surfactant loading is based on the massof the continuous phase. % RF solution is the mass of (Resorcinol,Formaldehyde (including water), additional water and acid.) over thetotal mass of Resorcinol, Formaldehyde (including water), additionalwater, acid and continuous phase

Other more specific methods according to the instant disclosure includea method for preparing a condensation polymer, the method comprising:

a) preparing an emulsion, suspension or combination thereof by admixinga surfactant, one or more polymer precursors and a first and secondsolvent, wherein the first and second solvents are not miscible witheach other; and

b) aging the emulsion at a temperature and for a time sufficient for theone or more polymer precursors to react with each other and form acondensation polymer.

In certain embodiments of the foregoing, the polymer precursors areselected from an alcohol, a phenol, a polyalcohol, a sugar, an alkylamine, an aromatic amine, an aldehyde, a ketone, a carboxylic acid, anester, a urea, an acid halide and an isocyanate.

In some embodiments, at least one polymer precursor is a phenoliccompound. For example, in some embodiments at least one polymerprecursor is resorcinol. In still other embodiments at least one polymerprecursor is phenol. In other examples, at least one polymer precursoris an aldehyde compound, for example, at least one polymer precursor maybe formaldehyde.

In some more specific embodiments, at least one polymer precursor isformaldehyde, at least one polymer precursor is resorcinol and thecondensation polymer is a resorcinol-formaldehyde polymer.

In some embodiments at least one polymer precursor is urea, and in otherembodiments at least one polymer precursor is melamine.

The foregoing method may further comprise including an electrochemicalmodifier, such as silicon or nitrogen, in the emulsion.

The various reaction parameters, including choice of polymer precursor,solvent, etc., of the method for preparing a condensation polymer can bemodified as described in the above section to obtain condensationpolymers having various properties.

2. Creation of Polymer Gel Particles

In contrast to prior monolith techniques, the presently disclosedmethods generally do not require milling or grinding prior to furtherprocessing. Instead, the polymer gel particles are generally filteredand/or the solvent removed by decanting and the gel particles areoptionally dried (e.g., freeze drying) prior to further processing.

3. Rapid Freezing of Polymer Gels

As noted above, certain embodiments of the method include freeze dryingprior to pyrolysis and/or activation; however such drying is optionaland is not included in some of the disclosed embodiments. Freezing ofthe polymer gel particles may be accomplished rapidly and in amulti-directional fashion as described in more detail above. Freezingslowly and in a unidirectional fashion, for example by shelf freezing ina lyophilizer, results in dried material having a very low surface area.Similarly, snap freezing (i.e., freezing that is accomplished by rapidlycooling the polymer gel particles by pulling a deep vacuum) also resultsin a dried material having a low surface area. As disclosed herein rapidfreezing in a multidirectional fashion can be accomplished by rapidlylowering the material temperature to at least about −10° C. or lower,for example, −20° C. or lower, or for example, to at least about −30° C.or lower. Rapid freezing of the polymer gel particles creates a fine icecrystal structure within the particles due to widespread nucleation ofice crystals, but leaves little time for ice crystal growth. Thisprovides a high specific surface area between the ice crystals and thehydrocarbon matrix, which is necessarily excluded from the ice matrix.

The concept of extremely rapid freezing to promote nucleation overcrystal growth can also be applied to mixed solvent systems. In oneembodiment, as the mixed solvent system is rapidly cooled, the solventcomponent that predominates will undergo crystallization at itsequilibrium melting temperature, with increased concentration of theco-solvent(s) and concomitant further freezing point depression. As thetemperature is further lowered, there is increased crystallization ofthe predominant solvent and concentration of co-solvent(s) until theeutectic composition is reached, at which point the eutectic compositionundergoes the transition from liquid to solid without further componentconcentration or product cooling until complete freezing is achieved. Inthe specific case of water and acetic acid (which as pure substancesexhibit freezing points of 0° C. and 17° C., respectively), the eutecticcomposition is comprised of approximately 59% acetic acid and 41% waterand freezes at about −27° C. Accordingly, in one embodiment, the mixedsolvent system is the eutectic composition, for example, in oneembodiment the mixed solvent system comprises 59% acetic acid and 41%water.

4. Drying of Polymer Gels

Some embodiments include an optional drying step. In one embodiment, thefrozen polymer gel particles containing a fine ice matrix arelyophilized under conditions designed to avoid collapse of the materialand to maintain fine surface structure and porosity in the driedproduct. Generally drying is accomplished under conditions where thetemperature of the product is kept below a temperature that wouldotherwise result in collapse of the product pores, thereby enabling thedried material to retain the desired surface area.

The structure of the final carbon material is reflected in the structureof the dried polymer gel which in turn is established by the polymer gelproperties. These features can be created in the polymer gel using asol-gel processing approach as described herein, but if care is nottaken in removal of the solvent, then the structure is not preserved. Itis of interest to both retain the original structure of the polymer geland modify its structure with ice crystal formation based on control ofthe freezing process. In some embodiments prior to drying, the aqueouscontent of the polymer gel is in the range of about 50% to about 99%. Incertain embodiments upon drying, the aqueous content of the polymercryogel is about 10%, alternately less than about 5% or less than about2.5%.

A lyophilizer chamber pressure of about 2250 microns results in aprimary drying temperature in the drying product of about −10° C. Dryingat about 2250 micron chamber pressure or lower case provides a producttemperature during primary drying that is no greater than about −10° C.As a further illustration, a chamber pressure of about 1500 micronsresults in a primary drying temperature in the drying product of about−15° C. Drying at about 1500 micron chamber pressure or lower provides aproduct temperature during primary drying that is no greater than about−15° C. As yet a further illustration, a chamber pressure of about 750microns results in a primary drying temperature in the drying product ofabout −20° C. Drying at 750 micron chamber pressure or lower provides aproduct temperature during primary drying that is no greater than about−20° C. As yet a further illustration, a chamber pressure of about 300microns results in a primary drying temperature in the drying product ofabout −30° C. Drying at 300 micron chamber pressure or lower provides aproduct temperature during primary drying that is no greater than about−30° C.

5. Pyrolysis and Activation of Polymer Gels

The polymer gels described above, can be further processed to obtaincarbon materials. Such processing includes, for example, pyrolysisand/or activation. Generally, in the pyrolysis process, dried polymergels are weighed and placed in a rotary kiln. The temperature ramp isset at 5° C. per minute, the dwell time and dwell temperature are set;cool down is determined by the natural cooling rate of the furnace. Theentire process is usually run under an inert atmosphere, such as anitrogen environment. Pyrolyzed samples are then removed and weighed.Other pyrolysis processes are well known to those of skill in the art.

In some embodiments, pyrolysis dwell time (the period of time duringwhich the sample is at the desired temperature) is from about 0 minutesto about 120 minutes, from about 20 minutes to about 150 minutes, fromabout 30 minutes to about 100 minutes, from about 50 minutes to about 60minutes or from about 55 minutes to about 60 minutes.

Pyrolysis may also be carried out more slowly than described above. Forexample, in one embodiment the pyrolysis is carried out in about 120 to480 minutes. In other embodiments, the pyrolysis is carried out in about120 to 240 minutes.

In some embodiments, the pyrolysis dwell temperature ranges from about500° C. to 2400° C. In some embodiments, the pyrolysis dwell temperatureranges from about 600° C. to 1800° C. In other embodiments the pyrolysisdwell temperature ranges from about 700° C. to about 1200° C. In otherembodiments the pyrolysis dwell temperature ranges from about 850° C. toabout 1050° C. In other embodiments the pyrolysis dwell temperatureranges from about 800° C. to about 900° C. In some embodiments, thepyrolysis dwell temperature is about 600° C. or 900° C. In some otherspecific embodiments, the pyrolysis dwell temperature ranges from about550° C. to about 900° C.

In some embodiments, the pyrolysis dwell temperature is varied duringthe course of pyrolysis. In one embodiment, the pyrolysis is carried outin a rotary kiln with separate, distinct heating zones. The temperaturefor each zone is sequentially decreased from the entrance to the exitend of the rotary kiln tube. In one embodiment, the pyrolysis is carriedout in a rotary kiln with separate distinct heating zones, and thetemperature for each zone is sequentially increased from entrance toexit end of the rotary kiln tube.

Activation time and activation temperature both have a large impact onthe performance of the resulting activated carbon material, as well asthe manufacturing cost thereof. Increasing the activation temperatureand the activation dwell time results in higher activation percentages,which generally correspond to the removal of more material compared tolower temperatures and shorter dwell times. Activation temperature canalso alter the pore structure of the carbon where lower temperaturesresult in more microporous carbon and higher temperatures result inmesoporosity. This is a result of the activation gas diffusion limitedreaction that occurs at higher temperatures and reaction kinetic drivenreactions that occur at lower temperature. Higher activation percentageoften increases performance of the final activated carbon, but it alsoincreases cost by reducing overall yield. Improving the level ofactivation corresponds to achieving a higher performance product at alower cost.

Pyrolyzed polymer gels may be activated by contacting the pyrolyzedpolymer gel with an activating agent. Many gases are suitable foractivating, for example gases which contain oxygen. Non-limitingexamples of activating gases include carbon dioxide, carbon monoxide,steam, oxygen and combinations thereof. Activating agents may alsoinclude corrosive chemicals such as acids, bases or salts (e.g.,phosphoric acid, acetic acid, citric acid, formic acid, oxalic acid,uric acid, lactic acid, potassium hydroxide, sodium hydroxide, zincchloride, etc.). Other activating agents are known to those skilled inthe art.

In some embodiments, the activation time is between 1 minute and 48hours. In other embodiments, the activation time is between 10 minuteand 24 hours. In other embodiments, the activation time is between 60minutes and 24 hours. In other embodiments, the activation time isbetween 2 hour and 24 hours. In further embodiments, the activation timeis between 12 hours and 24 hours. In certain other embodiments, theactivation time is between 30 min and 8 hours. In some furtherembodiments, the activation time is between 3 hour and 6 hours.

Pyrolyzed polymer gels may be activated using any number of suitableapparatuses known to those skilled in the art, for example, fluidizedbeds, rotary kilns, elevator kilns, roller hearth kilns, pusher kilns,etc. In one embodiment of the activation process, samples are weighedand placed in a rotary kiln, for which the automated gas controlmanifold is set to ramp at a 20° C. per minute rate. Carbon dioxide isintroduced to the kiln environment for a period of time once the properactivation temperature has been reached. After activation has occurred,the carbon dioxide is replaced by nitrogen and the kiln is cooled down.Samples are weighed at the end of the process to assess the level ofactivation. Other activation processes are well known to those of skillin the art. In some of the embodiments disclosed herein, activationtemperatures may range from 800° C. to 1300° C. In another embodiment,activation temperatures may range from 800° C. to 1050° C. In anotherembodiment, activation temperatures may range from about 850° C. toabout 950° C. In another embodiment, the activation temperature is about900° C. In some embodiments, the carbon materials are activated toachieve a specific surface area ranging from 1700 to 1900 m²/g. Oneskilled in the art will recognize that other activation temperatures,either lower or higher, may be employed.

The degree of activation is measured in terms of the mass percent of thepyrolyzed dried polymer gel that is lost during the activation step. Inone embodiment of the methods described herein, activating comprises adegree of activation from 5% to 90%; or a degree of activation from 10%to 80%; in some cases activating comprises a degree of activation from40% to 70%, or a degree of activation from 45% to 65%.

B. Properties of Polymer Gels

One embodiment of the present disclosure provides a polymer gel preparedby any of the methods disclosure herein. The polymer gels produced bythe disclosed methods are unique in many respects. In some embodiments,the method produces polymer gels having monodisperse or nearmonodisperse particle size distributions. As discussed above, theparticle size of the polymer gels (and carbon materials) can becontrolled by a number of process parameters, including the stirringrate. For example, in some embodiments the present disclosure provides apolymer gel having a particle size distribution such that(Dv,90−Dv,10)/Dv,50 is less than 3, wherein Dv,10, Dv,50 and Dv,90 arethe particle size at 10%, 50% and 90%, respectively of the particle sizedistribution by volume. In some embodiments, (Dv,90−Dv,10)/Dv,50 is lessthan 2 and in other embodiments (Dv90−Dv10)/Dv50 is less than 1.

The polymer gel particles are also substantially spherical in shape (seee.g., FIG. 14A). The spherical nature of the gels results in sphericalcarbon materials which in turn may contribute to desirableelectrochemical properties. In some embodiments, the polymer gelscomprise a plurality of polymer gel particles, wherein greater than 90%of the polymer gel particles have a spherical geometry. In otherembodiments, greater than 95% of the polymer gel particles have aspherical geometry. The particle size of the polymer particles in gelform can be expressed alternatively as the average cross-sectionallength. For the embodiment of spherical particles, the range of averagecross-sectional lengths for polymer particles in gel form in variousembodiments can mirror the embodiments described herein for the volumeaverage particle size (Dv,50). For other embodiments of non-sphericalparticles, the important dimension with regards to heat transfer andpolymerication within the particle is the minimum characteristic crosssectional length (for example, for rod-link particles the minimumcharacteristic cross sectional length is the rod diameter).

The specific surface area of the polymer gels as determined by BETanalysis ranges from about 50 m²/g to about 1000 m²/g. In someembodiments, the specific surface area ranges from about 50 m²/g toabout 100 m²/g. In other embodiments, the specific surface area rangesfrom about 300 m²/g to about 700 m²/g. In some other embodiments, thespecific surface area ranges from about 300 m²/g to about 400 m²/g. Insome other embodiments, the specific surface area ranges from about 400m²/g to about 500 m²/g. In some other embodiments, the specific surfacearea ranges from about 500 m²/g to about 600 m²/g. In some otherembodiments, the specific surface area ranges from about 600 m²/g toabout 700 m²/g.

The total pore volume of the polymer gels ranges from about 0.01 cc/g toabout 1.5 cc/g. For example, in some embodiments the total pore volumeranges from about 0.1 cc/g to about 0.9 cc/g. In other embodiments thetotal pore volume ranges from about 0.2 cc/g to about 0.8 cc/g. In otherembodiments the total pore volume ranges from about 0.3 cc/g to about0.6 cc/g. In other embodiments the total pore volume ranges from about0.6 cc/g to about 0.9 cc/g.

In other embodiments, the polymer gel comprises a total of less than 500ppm of all other elements having atomic numbers ranging from 11 to 92.For example, in some other embodiments the polymer gel comprises lessthan 200 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm,less than 10 ppm, less than 5 ppm or less than 1 ppm of all otherelements having atomic numbers ranging from 11 to 92. In someembodiments, the electrochemical modifier content and impurity contentof the polymer gels can be determined by proton induced x-ray emission(PUCE) analysis.

In some embodiments, the polymer gel is a dried polymer gel, forexample, a polymer cryogel. In other embodiments, the dried polymer gelis a polymer xerogel or a polymer aerogel. In some embodiments, thepolymer precursors are selected from aliphatic and aromatic alcohols,aliphatic and aromatic amines and carbonyl-containing compounds. Forexample, the polymer precursors may be selected from an alcohol, aphenol, a polyalcohol, a sugar, an alkyl amine, an aromatic amine, analdehyde, a ketone, a carboxylic acid, an ester, a urea, an acid halideand an isocyanate. In some specific embodiments, the polymer gels areprepared from phenolic compounds and aldehyde compounds, for example, inone embodiment, the polymer gels can be produced from resorcinol andformaldehyde. In some embodiments, acidity can be provided bydissolution of a solid acid compound, by employing an acid as thereaction solvent or by employing a mixed solvent system where one of thesolvents is an acid.

Some embodiments of the disclosed process comprise polymerization toform a polymer gel in the presence of a basic volatile catalyst.Accordingly, in some embodiments, the polymer gel comprises one or moresalts, for example, in some embodiments the one or more salts are basicvolatile salts. Examples of basic volatile salts include, but are notlimited to, ammonium carbonate, ammonium bicarbonate, ammonium acetate,ammonium hydroxide, and combinations thereof. Accordingly, in someembodiments, the present disclosure provides a polymer gel comprisingammonium carbonate, ammonium bicarbonate, ammonium acetate, ammoniumhydroxide, or combinations thereof. In further embodiments, the polymergel comprises ammonium carbonate. In other further embodiments, thepolymer gel comprises ammonium acetate.

The disclosed methods are useful for preparation polymer gels havinghigh purity as determined by PIXE analysis and/or ash content. Asdescribed herein, any intentionally added electrochemical modifier isnot considered an impurity and thus excluded from the specificallydescribed PIXE and ash content values. In some embodiments, the polymergels comprise low ash content which may contribute to the low ashcontent of a carbon material prepared therefrom. Thus, in someembodiments, the ash content of the polymer gel ranges from 0.1% to0.001%. In other embodiments, the ash content of the polymer gel is lessthan 0.1%, less than 0.08%, less than 0.05%, less than 0.03%, less than0.025%, less than 0.01%, less than 0.0075%, less than 0.005% or lessthan 0.001%.

In other embodiments, the polymer gel has a total PIXE impurity contentof less than 500 ppm and an ash content of less than 0.08%. In a furtherembodiment, the polymer gel has a total PIXE impurity content of lessthan 300 ppm and an ash content of less than 0.05%. In another furtherembodiment, the polymer gel has a total PIXE impurity content of lessthan 200 ppm and an ash content of less than 0.02%. In another furtherembodiment, the polymer gel has a total PIXE impurity content of lessthan 200 ppm and an ash content of less than 0.01%.

Polymer gels comprising impurities generally yield carbon materialswhich also comprise impurities, and thus potentially undesiredelectrochemical properties. Accordingly, one aspect of the presentdisclosure is a polymer gel prepared via the disclosed methods andhaving low levels of residual undesired impurities. The amount ofindividual PIXE impurities present in the polymer gel can be determinedby proton induced x-ray emission. In some embodiments, the level ofsodium present in the polymer gel is less than 1000 ppm, less than 500ppm, less than 100 ppm, less than 50 ppm, less than 10 ppm, or less than1 ppm. In some embodiments, the level of magnesium present in thepolymer gel is less than 1000 ppm, less than 100 ppm, less than 50 ppm,less than 10 ppm, or less than 1 ppm. As noted above, in someembodiments other impurities such as hydrogen, oxygen and/or nitrogenmay be present in levels ranging from less than 10% to less than 0.01%.

In some specific embodiments, the polymer gel comprises less than 100ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur, lessthan 100 ppm calcium, less than 20 ppm iron, less than 10 ppm nickel,less than 40 ppm copper, less than 5 ppm chromium and less than 5 ppmzinc. In other specific embodiments, the polymer gel comprises less than50 ppm sodium, less than 100 ppm silicon, less than 30 ppm sulfur, lessthan 50 ppm calcium, less than 10 ppm iron, less than 5 ppm nickel, lessthan 20 ppm copper, less than 2 ppm chromium and less than 2 ppm zinc.

In other specific embodiments, the polymer gel comprises less than 50ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur, less than10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel, less than1 ppm copper, less than 1 ppm chromium and less than 1 ppm zinc.

In some other specific embodiments, the polymer gel comprises less than100 ppm sodium, less than 50 ppm magnesium, less than 50 ppm aluminum,less than 10 ppm sulfur, less than 10 ppm chlorine, less than 10 ppmpotassium, less than 1 ppm chromium and less than 1 ppm manganese.

The disclosed method yields a polymer gel comprising various specificsurface areas depending on the exact reaction parameters. Without beingbound by theory, it is believed that the surface area of the polymer gelcontributes, at least in part, to the surface area properties of thecarbon materials. The surface area can be measured using the BETtechnique well-known to those of skill in the art. In one embodiment ofany of the aspects disclosed herein the polymer gel comprises a BETspecific surface area of at least 150 m²/g, at least 250 m²/g, at least400 m²/g, at least 500 m²/g, at least 600 m²/g, at least 700 m²/g, atleast 800 m²/g, or at least 900 m²/g, or at least 1000 m²/g, or at least1100 m²/g.

In one embodiment, the polymer gel comprises a BET specific surface areaof 100 m²/g to 1000 m²/g. Alternatively, the polymer gel comprises a BETspecific surface area of between 150 m²/g and 900 m²/g. Alternatively,the polymer gel comprises a BET specific surface area of between 400m²/g and 800 m²/g.

In one embodiment, the polymer gel comprises a tap density of from 0.10g/cc to 0.60 g/cc. In one embodiment, the polymer gel comprises a tapdensity of from 0.15 g/cc to 0.25 g/cc. In one embodiment of the presentdisclosure, the polymer gel comprises a BET specific surface area of atleast 150 m²/g and a tap density of less than 0.60 g/cc. Alternately,the polymer gel comprises a BET specific surface area of at least 250m²/g and a tap density of less than 0.4 g/cc. In another embodiment, thepolymer gel comprises a BET specific surface area of at least 500 m²/gand a tap density of less than 0.30 g/cc.

In another embodiment of any of the aspects or variations disclosedherein the polymer gel comprises a residual water content of less than15%, less than 13%, less than 10%, less than 5% or less than 1%.

In one embodiment, the polymer gel comprises a fractional pore volume ofpores at or below 500 angstroms that comprises at least 25% of the totalpore volume, 50% of the total pore volume, at least 75% of the totalpore volume, at least 90% of the total pore volume or at least 99% ofthe total pore volume. In another embodiment, the polymer gel comprisesa fractional pore volume of pores at or below 20 nm that comprises atleast 50% of the total pore volume, at least 75% of the total porevolume, at least 90% of the total pore volume or at least 99% of thetotal pore volume.

In some embodiments, the amount of nitrogen adsorbed per mass of polymergel at 0.05 relative pressure is at least 10% of the total nitrogenadsorbed up to 0.99 relative pressure or at least 20% of the totalnitrogen adsorbed up to 0.99 relative pressure. In another embodiment,the amount of nitrogen adsorbed per mass of polymer gel at 0.05 relativepressure is between 10% and 50% of the total nitrogen adsorbed up to0.99 relative pressure, is between 20% and 60% of the total nitrogenadsorbed up to 0.99 relative pressure or is between 20% and 30% of thetotal nitrogen adsorbed up to 0.99 relative pressure.

In one embodiment, the polymer gel comprises a fractional pore surfacearea of pores at or below 100 nm that comprises at least 50% of thetotal pore surface area, at least 75% of the total pore surface area, atleast 90% of the total pore surface area or at least 99% of the totalpore surface area. In another embodiment, the polymer gel comprises afractional pore surface area of pores at or below 20 nm that comprisesat least 50% of the total pore surface area, at least 75% of the totalpore surface area, at least 90% of the total pore surface or at least99% of the total pore surface area.

As described in more detail above, methods for preparing the disclosedcarbon materials may include pyrolysis of a polymer gel. In someembodiments, the pyrolyzed polymer gels have a surface area from about100 to about 1200 m²/g. In other embodiments, the pyrolyzed polymer gelshave a surface area from about 500 to about 800 m²/g. In otherembodiments, the pyrolyzed polymer gels have a surface area from about500 to about 700 m²/g.

In other embodiments, the pyrolyzed polymer gels have a tap density fromabout 0.1 to about 1.0 g/cc. In other embodiments, the pyrolyzed polymergels have a tap density from about 0.3 to about 0.6 g/cc. In otherembodiments, the pyrolyzed polymer gels have a tap density from about0.3 to about 0.5 g/cc.

In some embodiments, the polymer gels exhibit a mean particle diameterranging from about 4 μm to about 4 mm. In other embodiments, the meanparticle diameter ranges from about 1 μm to about 1 mm. In otherembodiments, the mean particle diameter ranges from about 10 μm to about1 mm. Yet in other embodiments, the mean particle diameter ranges fromabout 20 μm to about 500 μm. Still in other embodiments, the meanparticle diameter ranges from about 500 μm to about 4 mm. Yet still inother embodiments, the mean particle diameter ranges from about 2 μm toabout 300 μm. In other embodiments, the mean particle diameter rangesfrom about 100 μm to about 10 μm. In some embodiments, the mean particlediameter is about 0.9 mm, about 0.8 mm or about 0.5 mm. In otherembodiments, the mean particle diameter is about 100 μm, about 50 μm orabout 10 μm.

In still other embodiments, the polymer gels comprise a monodisperse, ornear monodisperse particle size distribution. For example, in someembodiments the polymer gels have a particle size distribution such that(Dv,90−Dv,10)/Dv,50 is less than 3, wherein Dv,10, Dv,50 and Dv,90 arethe particle size at 10%, 50% and 90%, respectively of the particle sizedistribution by volume. In further embodiments, (Dv,90−Dv,10)/Dv,50 isless than 2 or even less than 1. In still other embodiments,(Dv,90−Dv,10)/Dv,50 is less than 1,000, less than 100, less than 10,less than 5, less than 3, less than 2, less than 1.5 or even less than1.

In yet other embodiments, the polymer gel particles have a substantiallyspherical geometry (see e.g., FIG. 23A). Such geometry contributes to aspherical geometry in some embodiments of the resulting carbon particlesas discussed in more detail below. In some embodiments, the polymer gelscomprise a plurality of polymer gel particles, wherein greater than 90%of the polymer gel particles have a spherical geometry. For example, insome embodiments, greater than 95% of the polymer gel particles have aspherical geometry.

Since the polymer gels may comprise electrochemical modifiers, theelemental content of the gels may vary. In some embodiments, the polymergels comprise greater than about 100 ppm of an electrochemical modifier.In certain embodiments, the electrochemical modifier is selected fromnitrogen, iron, tin, silicon, nickel, aluminum and manganese. In someembodiments, the electrochemical modifier is silicon and in otherembodiments the electrochemical modifier is nitrogen.

The amount of electrochemical modifier in the polymer gels is controlledto a level desirable for the final carbon material. Accordingly, in someembodiments, the polymer gel comprises at least 0.10%, at least 0.25%,at least 0.50%, at least 1.0%, at least 5.0%, at least 10%, at least25%, at least 50%, at least 75%, at least 90%, at least 95%, at least99% or at least 99.5% of the electrochemical modifier. For example, insome embodiments, the polymer gels comprise between 0.5% and 99.5%carbon and between 0.5% and 99.5% electrochemical modifier. The percentof the electrochemical modifier is calculated on weight percent basis(wt %).

C. Properties of Carbon Materials

One embodiment of the present disclosure provides a carbon materialprepared by any of the methods disclosed herein. The pore sizedistribution of the carbon materials may contribute to the superiorperformance of electrical devices comprising the carbon materialsrelative to devices comprising other known carbon materials. Forexample, in some embodiments, the carbon material comprises an optimizedblend of both micropores and mesopores and may also comprise low surfacefunctionality upon pryolysis and/or activation. In other embodiments,the carbon material comprises a total of less than 500 ppm of allelements having atomic numbers ranging from 11 to 92, as measured byproton induced x-ray emission. The high purity and optimized microporeand/or mesopore distribution make the carbon materials ideal for use inelectrical storage and distribution devices, for exampleultracapacitors.

While not wishing to be bound by theory, Applicants believe theoptimized pore size distributions, as well as the high purity, of thedisclosed carbon materials can be attributed, at least in part, to thedisclosed emulsion/suspension polymerization methods. The properties ofthe disclosed carbon materials, as well as methods for their preparationare discussed in more detail below.

While not wishing to be bound by theory, it is believed that, inaddition to the pore structure, the purity profile, surface area andother properties of the carbon materials are a function of itspreparation method, and variation of the preparation parameters mayyield carbon materials having different properties. Accordingly, in someembodiments, the carbon material is a pyrolyzed dried polymer gel, forexample, a pyrolyzed polymer cryogel, a pyrolyzed polymer xerogel or apyrolyzed polymer aerogel. In other embodiments, the carbon material ispyrolyzed and activated (e.g., a synthetic activated carbon material).For example, in further embodiments the carbon material is an activateddried polymer gel, an activated polymer cryogel, an activated polymerxerogel or an activated polymer aerogel.

As noted above, activated carbon particles are widely employed as anenergy storage material. In this regard, a critically importantcharacteristic is high power density, which is possible with electrodesthat have low ionic resistance that yield high frequency response. It isimportant to achieve a low ionic resistance, for instance in situationswith device ability to respond to cyclic performance is a constraint.The disclosed methods are useful for preparing carbon material thatsolves the problem of how to optimize an electrode formulation andmaximize the power performance of electrical energy storage anddistribution devices. Devices comprising the carbon materials exhibitlong-term stability, fast response time and high pulse powerperformance.

In some embodiments, the disclosed methods produce carbon materialscomprising micropore and/or mesopore structure, which is typicallydescribed in terms of fraction (percent) of total pore volume residingin either micropores or mesopores or both. Accordingly, in someembodiments the pore structure of the carbon materials comprises from20% to 90% micropores. In other embodiments, the pore structure of thecarbon materials comprises from 30% to 70% micropores. In otherembodiments, the pore structure of the carbon materials comprises from40% to 60% micropores. In other embodiments, the pore structure of thecarbon materials comprises from 40% to 50% micropores. In otherembodiments, the pore structure of the carbon materials comprises from43% to 47% micropores. In certain embodiments, the pore structure of thecarbon materials comprises about 45% micropores.

The mesoporosity of the carbon materials may contribute to high ionmobility and low resistance. In some embodiments, the pore structure ofthe carbon materials comprises from 20% to 80% mesopores. In otherembodiments, the pore structure of the carbon materials comprises from30% to 70% mesopores. In other embodiments, the pore structure of thecarbon materials comprises from 40% to 60% mesopores. In otherembodiments, the pore structure of the carbon materials comprises from50% to 60% mesopores. In other embodiments, the pore structure of thecarbon materials comprises from 53% to 57% mesopores. In otherembodiments, the pore structure of the carbon materials comprises about55% mesopores.

An optimized blend of micropores and mesopores within the carbonmaterials may contribute to the enhanced electrochemical performance ofthe same. Thus, in some embodiments the pore structure of the carbonmaterials comprises from 20% to 80% micropores and from 20% to 80%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 30% to 70% micropores and from 30% to 70%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 40% to 60% micropores and from 40% to 60%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 40% to 50% micropores and from 50% to 60%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 43% to 47% micropores and from 53% to 57%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises about 45% micropores and about 55% mesopores.

In other variations, the carbon materials do not have a substantialvolume of pores greater than 20 nm. For example, in certain embodimentsthe carbon materials comprise less than 25%, less than 20%, less than15%, less than 10%, less than 5%, less than 2.5% or even less than 1% ofthe total pore volume in pores greater than 20 nm.

The porosity of the carbon materials contributes to their enhancedelectrochemical performance. Accordingly, in one embodiment the carbonmaterial comprises a pore volume residing in pores less than 20angstroms of at least 1.8 cc/g, at least 1.2, at least 0.6, at least0.30 cc/g, at least 0.25 cc/g, at least 0.20 cc/g or at least 0.15 cc/g.In other embodiments, the carbon material comprises a pore volumeresiding in pores greater than 20 angstroms of at least 7 cc/g, at least5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g, at least 3.50 cc/g, atleast 3.25 cc/g, at least 3.00 cc/g, at least 2.75 cc/g, at least 2.50cc/g, at least 2.25 cc/g, at least 2.00 cc/g, at least 1.90 cc/g, 1.80cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40 cc/g, at least 1.30 cc/g, atleast 1.20 cc/g, at least 1.10 cc/g, at least 1.00 cc/g, at least 0.85cc/g, at least 0.80 cc/g, at least 0.75 cc/g, at least 0.70 cc/g, atleast 0.65 cc/g, at least 0.50 cc/g, at least 0.4 cc/g, at least 0.2cc/g or at least 0.1 cc/g.

In other embodiments, the carbon material comprises a pore volume of atleast 7.00 cc/g, at least 5.00 cc/g, at least 4.00 cc/g, at least 3.75cc/g, at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, atleast 2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00cc/g, at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, atleast 1.40 cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0cc/g, at least 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least0.2 cc/g or at least 0.1 cc/g for pores ranging from 20 angstroms to 500angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast at least 7.00 cc/g, at least 5.00 cc/g, 4.00 cc/g, at least 3.75cc/g, at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, atleast 2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00cc/g, at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g,1.40 cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.10 cc/g,at least 1.00 cc/g, at least 0.85 cc/g, at least 0.80 cc/g, at least0.75 cc/g, at least 0.70 cc/g, at least 0.65 cc/g, at least 0.50 cc/g,at least 1.40 cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0cc/g, at least 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least0.2 cc/g or at least 0.1 cc/g for pores ranging from 20 angstroms to 300angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 1000 angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 2000 angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 5000 angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 1 micron.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 2 microns.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 3 microns.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 4 microns.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 5 microns.

In yet other embodiments, the carbon materials comprise a total porevolume of at least 4.00 cc/g, at least 3.75 cc/g, at least 3.50 cc/g, atleast 3.25 cc/g, at least 3.00 cc/g, at least 2.75 cc/g, at least 2.50cc/g, at least 2.25 cc/g, at least 2.00 cc/g, at least 1.90 cc/g, 1.80cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40 cc/g, at least 1.30 cc/g, atleast 1.20 cc/g, at least 1.10 cc/g, at least 1.00 cc/g, at least 0.85cc/g, at least 0.80 cc/g, at least 0.75 cc/g, at least 0.70 cc/g, atleast 0.65 cc/g, at least 0.60 cc/g, at least 0.55 cc/g, at least 0.50cc/g, at least 0.45 cc/g, at least 0.40 cc/g, at least 0.35 cc/g, atleast 0.30 cc/g, at least 0.25 cc/g, at least 0.20 cc/g or at least 0.10cc/g.

In yet other embodiments, the carbon materials comprise a pore volumeresiding in pores of less than 20 angstroms of at least 0.2 cc/g and apore volume residing in pores of between 20 and 300 angstroms of atleast 0.8 cc/g. In yet other embodiments, the carbon materials comprisea pore volume residing in pores of less than 20 angstroms of at least0.5 cc/g and a pore volume residing in pores of between 20 and 300angstroms of at least 0.5 cc/g. In yet other embodiments, the carbonmaterials comprise a pore volume residing in pores of less than 20angstroms of at least 0.6 cc/g and a pore volume residing in pores ofbetween 20 and 300 angstroms of at least 2.4 cc/g. In yet otherembodiments, the carbon materials comprise a pore volume residing inpores of less than 20 angstroms of at least 1.5 cc/g and a pore volumeresiding in pores of between 20 and 300 angstroms of at least 1.5 cc/g.

In some embodiments, the pores of the carbon material comprise a peakpore volume ranging from 2 nm to 10 nm. In other embodiments, the peakpore volume ranges from 10 nm to 20 nm. Yet in other embodiments, thepeak pore volume ranges from 20 nm to 30 nm. Still in other embodiments,the peak pore volume ranges from 30 nm to 40 nm. Yet still in otherembodiments, the peak pore volume ranges from 40 nm to 50 nm. In otherembodiments, the peak pore volume ranges from 50 nm to 100 nm.

In certain embodiments a mesoporous carbon material having low porevolume in the micropore region (e.g., less than 60%, less than 50%, lessthan 40%, less than 30%, less than 20% microporosity) is prepared by thedisclosed methods. For example, the mesoporous carbon can be a polymergel that has been pyrolyzed, but not activated. In some embodiments, thepyrolyzed mesoporous carbon comprises a specific surface area of atleast 400 m²/g, at least 500 m²/g, at least 600 m²/g, at least 675 m²/gor at least 750 m²/g. In other embodiments, the mesoporous carbonmaterial comprises a total pore volume of at least 0.50 cc/g, at least0.60 cc/g, at least 0.70 cc/g, at least 0.80 cc/g or at least 0.90 cc/g.In yet other embodiments, the mesoporous carbon material comprises a tapdensity of at least 0.30 g/cc, at least 0.35 g/cc, at least 0.40 g/cc,at least 0.45 g/cc, at least 0.50 g/cc or at least 0.55 g/cc.

In other embodiments, the carbon materials comprise a total pore volumeranging greater than or equal to 0.1 cc/g, and in other embodiments thecarbon materials comprise a total pore volume less than or equal to 0.6cc/g. In other embodiments, the carbon materials comprise a total porevolume ranging from about 0.1 cc/g to about 0.6 cc/g. In some otherembodiments, the total pore volume of the carbon materials ranges fromabout 0.1 cc/g to about 0.2 cc/g. In some other embodiments, the totalpore volume of the carbon materials ranges from about 0.2 cc/g to about0.3 cc/g. In some other embodiments, the total pore volume of the carbonmaterials ranges from about 0.3 cc/g to about 0.4 cc/g. In some otherembodiments, the total pore volume of the carbon materials ranges fromabout 0.4 cc/g to about 0.5 cc/g. In some other embodiments, the totalpore volume of the carbon materials ranges from about 0.5 cc/g to about0.6 cc/g.

The carbon material comprises low total PIXE impurities. Thus, in someembodiments the total PIXE impurity content of all other PIXE elementsin the carbon material (as measured by proton induced x-ray emission) isless than 1000 ppm. In other embodiments, the total PIXE impuritycontent of all other PIXE elements in the carbon material is less than800 ppm, less than 500 ppm, less than 300 ppm, less than 200 ppm, lessthan 150 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm,less than 10 ppm, less than 5 ppm or less than 1 ppm. In furtherembodiments of the foregoing, the carbon material is a pyrolyzed driedpolymer gel, a pyrolyzed polymer cryogel, a pyrolyzed polymer xerogel, apyrolyzed polymer aerogel, an activated dried polymer gel, an activatedpolymer cryogel, an activated polymer xerogel or an activated polymeraerogel.

In addition to low content of undesired PIXE impurities, the disclosedcarbon materials may comprise high total carbon content. In addition tocarbon, the carbon material may also comprise oxygen, hydrogen, nitrogenand the electrochemical modifier. In some embodiments, the materialcomprises at least 75% carbon, 80% carbon, 85% carbon, at least 90%carbon, at least 95% carbon, at least 96% carbon, at least 97% carbon,at least 98% carbon or at least 99% carbon on a weight/weight basis. Insome other embodiments, the carbon material comprises less than 10%oxygen, less than 5% oxygen, less than 3.0% oxygen, less than 2.5%oxygen, less than 1% oxygen or less than 0.5% oxygen on a weight/weightbasis. In other embodiments, the carbon material comprises less than 10%hydrogen, less than 5% hydrogen, less than 2.5% hydrogen, less than 1%hydrogen, less than 0.5% hydrogen or less than 0.1% hydrogen on aweight/weight basis. In other embodiments, the carbon material comprisesless than 5% nitrogen, less than 2.5% nitrogen, less than 1% nitrogen,less than 0.5% nitrogen, less than 0.25% nitrogen or less than 0.01%nitrogen on a weight/weight basis. The oxygen, hydrogen and nitrogencontent of the disclosed carbon materials can be determined bycombustion analysis. Techniques for determining elemental composition bycombustion analysis are well known in the art.

In other embodiments, the carbon content is greater than 98 wt. % asmeasured by CHNO analysis. In another embodiment, the carbon contentranges from 50 to 98 wt. % of the total mass. In yet other embodiments,the carbon content ranges 90 to 98 wt. % of the total mass. In yet otherembodiments, the carbon content ranges from 80 to 90 wt. % of the totalmass. In yet other embodiments, the carbon content ranges from 70 to 80wt. % of the total mass. In yet other embodiments, the carbon contentranges from 60 to 70 wt. % of the total mass.

In another embodiment, the nitrogen content ranges from 0 to 30 wt. % asmeasured by CHNO analysis. In another embodiment, the nitrogen contentranges from 1 to 10 wt. % of the total mass. In yet other embodiments,the nitrogen content ranges from 10 to 20 wt. % of the total mass. Inyet other embodiments, the nitrogen content ranges from 20 to 30 wt. %of the total mass. In another embodiment, the nitrogen content isgreater than 30 wt. %.

The carbon and nitrogen content may also be measured as a ratio of C:N.In one embodiment, the C:N ratio ranges from 1:0.001 to 1:1. In anotherembodiment, the C:N ratio ranges from 1:0.001 to 0.01. In yet anotherembodiment, the C:N ratio ranges from 1:0.01 to 1:1. In yet anotherembodiment, the content of nitrogen exceeds the content of carbon.

The carbon materials may also comprise an electrochemical modifier(i.e., a dopant) selected to optimize the electrochemical performance ofthe carbon materials. The electrochemical modifier may be added duringthe polymerization step as described above. For example, theelectrochemical modifier may added to the above described mixture,continuous phase or polymer phase, or included within the polymerizationprocess in any other manner.

The electrochemical modifier may be incorporated within the porestructure and/or on the surface of the carbon material or incorporatedin any number of other ways. For example, in some embodiments, thecarbon materials comprise a coating of the electrochemical modifier(e.g., Al₂O₃) on the surface of the carbon materials. In someembodiments, the carbon materials comprise greater than about 100 ppm ofan electrochemical modifier. In certain embodiments, the electrochemicalmodifier is selected from iron, tin, silicon, nickel, aluminum andmanganese. In some embodiments, the electrochemical modifier is siliconand in other embodiments the electrochemical modifier is nitrogen.

In certain embodiments the electrochemical modifier comprises an elementwith the ability to lithiate from 3 to 0 V versus lithium metal (e.g.silicon, tin, sulfur). In other embodiments, the electrochemicalmodifier comprises metal oxides with the ability to lithiate from 3 to 0V versus lithium metal (e.g. iron oxide, molybdenum oxide, titaniumoxide). In still other embodiments, the electrochemical modifiercomprises elements which do not lithiate from 3 to 0 V versus lithiummetal (e.g. aluminum, manganese, nickel, metal-phosphates). In yet otherembodiments, the electrochemical modifier comprises a non-metal element(e.g. fluorine, nitrogen, hydrogen). In still other embodiments, theelectrochemical modifier comprises any of the foregoing electrochemicalmodifiers or any combination thereof (e.g. tin-silicon, nickel-titaniumoxide).

The electrochemical modifier may be provided in any number of forms. Forexample, in some embodiments the electrochemical modifier comprises asalt. In other embodiments, the electrochemical modifier comprises oneor more elements in elemental form, for example elemental iron, tin,silicon, nickel or manganese. In other embodiments, the electrochemicalmodifier comprises one or more elements in oxidized form, for exampleiron oxides, tin oxides, silicon oxides, nickel oxides, aluminum oxidesor manganese oxides.

In other embodiments, the electrochemical modifier comprises iron. Inother embodiments, the electrochemical modifier comprises tin. In otherembodiments, the electrochemical modifier comprises silicon. In someother embodiments, the electrochemical modifier comprises nickel. In yetother embodiments, the electrochemical modifier comprises aluminum. Inyet other embodiments, the electrochemical modifier comprises manganese.In yet other embodiments, the electrochemical modifier comprises Al₂O₃.

The electrochemical properties of the carbon materials can be modified,at least in part, by the amount of the electrochemical modifier in thecarbon material. Accordingly, in some embodiments, the carbon materialcomprises at least 0.10%, at least 0.25%, at least 0.50%, at least 1.0%,at least 5.0%, at least 10%, at least 25%, at least 50%, at least 75%,at least 90%, at least 95%, at least 99% or at least 99.5% of theelectrochemical modifier. For example, in some embodiments, the carbonmaterials comprise between 0.5% and 99.5% carbon and between 0.5% and99.5% electrochemical modifier. The percent of the electrochemicalmodifier is calculated on weight percent basis (wt %). In some othermore specific embodiments, the electrochemical modifier is selected fromiron, tin, silicon, nickel and manganese.

The total ash content of the carbon material may, in some instances,have an effect on the electrochemical performance of the carbonmaterial. Accordingly, in some embodiments, the ash content of thecarbon material ranges from 0.1% to 0.001% weight percent ash, forexample in some specific embodiments the ash content of the carbonmaterial is less than 0.1%, less than 0.08%, less than 0.05%, less than0.03%, than 0.025%, less than 0.01%, less than 0.0075%, less than 0.005%or less than 0.001%.

In other embodiments, the carbon material comprises a total PIXEimpurity content of less than 500 ppm and an ash content of less than0.08%. In further embodiments, the carbon material comprises a totalPIXE impurity content of less than 300 ppm and an ash content of lessthan 0.05%. In other further embodiments, the carbon material comprisesa total PIXE impurity content of less than 200 ppm and an ash content ofless than 0.05%. In other further embodiments, the carbon materialcomprises a total PIXE impurity content of less than 200 ppm and an ashcontent of less than 0.025%. In other further embodiments, the carbonmaterial comprises a total PIXE impurity content of less than 100 ppmand an ash content of less than 0.02%. In other further embodiments, thecarbon material comprises a total PIXE impurity content of less than 50ppm and an ash content of less than 0.01%.

The amount of individual PIXE impurities present in the disclosed carbonmaterials can be determined by proton induced x-ray emission. IndividualPIXE impurities may contribute in different ways to the overallelectrochemical performance of the disclosed carbon materials. Thus, insome embodiments, the level of sodium present in the carbon material isless than 1000 ppm, less than 500 ppm, less than 100 ppm, less than 50ppm, less than 10 ppm, or less than 1 ppm. As noted above, in someembodiments other impurities such as hydrogen, oxygen and/or nitrogenmay be present in levels ranging from less than 10% to less than 0.01%.

In some embodiments, the carbon material comprises undesired PIXEimpurities near or below the detection limit of the proton induced x-rayemission analysis. For example, in some embodiments the carbon materialcomprises less than 50 ppm sodium, less than 15 ppm magnesium, less than10 ppm aluminum, less than 8 ppm silicon, less than 4 ppm phosphorous,less than 3 ppm sulfur, less than 3 ppm chlorine, less than 2 ppmpotassium, less than 3 ppm calcium, less than 2 ppm scandium, less than1 ppm titanium, less than 1 ppm vanadium, less than 0.5 ppm chromium,less than 0.5 ppm manganese, less than 0.5 ppm iron, less than 0.25 ppmcobalt, less than 0.25 ppm nickel, less than 0.25 ppm copper, less than0.5 ppm zinc, less than 0.5 ppm gallium, less than 0.5 ppm germanium,less than 0.5 ppm arsenic, less than 0.5 ppm selenium, less than 1 ppmbromine, less than 1 ppm rubidium, less than 1.5 ppm strontium, lessthan 2 ppm yttrium, less than 3 ppm zirconium, less than 2 ppm niobium,less than 4 ppm molybdenum, less than 4 ppm, technetium, less than 7 ppmrubidium, less than 6 ppm rhodium, less than 6 ppm palladium, less than9 ppm silver, less than 6 ppm cadmium, less than 6 ppm indium, less than5 ppm tin, less than 6 ppm antimony, less than 6 ppm tellurium, lessthan 5 ppm iodine, less than 4 ppm cesium, less than 4 ppm barium, lessthan 3 ppm lanthanum, less than 3 ppm cerium, less than 2 ppmpraseodymium, less than 2 ppm, neodymium, less than 1.5 ppm promethium,less than 1 ppm samarium, less than 1 ppm europium, less than 1 ppmgadolinium, less than 1 ppm terbium, less than 1 ppm dysprosium, lessthan 1 ppm holmium, less than 1 ppm erbium, less than 1 ppm thulium,less than 1 ppm ytterbium, less than 1 ppm lutetium, less than 1 ppmhafnium, less than 1 ppm tantalum, less than 1 ppm tungsten, less than1.5 ppm rhenium, less than 1 ppm osmium, less than 1 ppm iridium, lessthan 1 ppm platinum, less than 1 ppm silver, less than 1 ppm mercury,less than 1 ppm thallium, less than 1 ppm lead, less than 1.5 ppmbismuth, less than 2 ppm thorium, or less than 4 ppm uranium.

In some specific embodiments, the carbon material comprises less than100 ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur, lessthan 100 ppm calcium, less than 20 ppm iron, less than 10 ppm nickel,less than 140 ppm copper, less than 5 ppm chromium and less than 5 ppmzinc as measured by proton induced x-ray emission. In other specificembodiments, the carbon material comprises less than 50 ppm sodium, lessthan 30 ppm sulfur, less than 100 ppm silicon, less than 50 ppm calcium,less than 10 ppm iron, less than 5 ppm nickel, less than 20 ppm copper,less than 2 ppm chromium and less than 2 ppm zinc.

In other specific embodiments, the carbon material comprises less than50 ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur, lessthan 10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel, lessthan 1 ppm copper, less than 1 ppm chromium and less than 1 ppm zinc.

In some other specific embodiments, the carbon material comprises lessthan 100 ppm sodium, less than 50 ppm magnesium, less than 50 ppmaluminum, less than 10 ppm sulfur, less than 10 ppm chlorine, less than10 ppm potassium, less than 1 ppm chromium and less than 1 ppmmanganese.

The disclosed carbon materials may also comprise a high surface area.While not wishing to be bound by theory, it is thought that the highsurface area may contribute, at least in part, to their superiorelectrochemical performance. Accordingly, in some embodiments, thecarbon material comprises a BET specific surface area of at least 100m²/g, at least 300 m²/g, at least 500 m²/g, at least 1000 m²/g, at least1500 m²/g, at least 2000 m²/g, at least 2400 m²/g, at least 2500 m²/g,at least 2750 m²/g or at least 3000 m²/g. In other embodiments, the BETspecific surface area ranges from about 100 m²/g to about 3000 m²/g, forexample from about 500 m²/g to about 1000 m²/g, from about 1000 m²/g toabout 1500 m²/g, from about 1500 m²/g to about 2000 m²/g, from about2000 m²/g to about 2500 m²/g or from about 2500 m²/g to about 3000 m²/g.For example, in some embodiments of the foregoing, the carbon materialis activated.

In some specific embodiments the surface area ranges from about 50 m²/gto about 1200 m²/g for example from about 50 m²/g to about 400 m²/g. Inother particular embodiments, the surface area ranges from about 200m²/g to about 300 m²/g for example the surface area may be about 250m²/g.

In another embodiment, the carbon material comprises a tap densitybetween 0.1 and 1.0 g/cc, between 0.2 and 0.8 g/cc, between 0.3 and 0.5g/cc or between 0.4 and 0.5 g/cc. In another embodiment, the carbonmaterial has a total pore volume of at least 0.1 cm³/g, at least 0.2cm³/g, at least 0.3 cm³/g, at least 0.4 cm3/g, at least 0.5 cm³/g, atleast 0.7 cm³/g, at least 0.75 cm³/g, at least 0.9 cm³/g, at least 1.0cm³/g, at least 1.1 cm³/g, at least 1.2 cm³/g, at least 1.3 cm³/g, atleast 1.4 cm³/g, at least 1.5 cm³/g or at least 1.6 cm³/g.

The pore size distribution of the disclosed carbon materials is oneparameter that may have an effect on the electrochemical performance ofthe carbon materials. For example, the carbon materials may comprisemesopores with a short effective length (i.e., less than 10 nm, lessthan 5, nm or less than 3 nm as measured by TEM) which decreases iondiffusion distance and may be useful to enhance ion transport andmaximize power. Accordingly, in one embodiment, the carbon materialcomprises a fractional pore volume of pores at or below 100 nm thatcomprises at least 50% of the total pore volume, at least 75% of thetotal pore volume, at least 90% of the total pore volume or at least 99%of the total pore volume. In other embodiments, the carbon materialcomprises a fractional pore volume of pores at or below 20 nm thatcomprises at least 50% of the total pore volume, at least 75% of thetotal pore volume, at least 90% of the total pore volume or at least 99%of the total pore volume.

In another embodiment, the carbon material comprises a fractional poresurface area of pores between 20 and 300 angstroms that comprises atleast 40% of the total pore surface area, at least 50% of the total poresurface area, at least 70% of the total pore surface area or at least80% of the total pore surface area. In another embodiment, the carbonmaterial comprises a fractional pore surface area of pores at or below20 nm that comprises at least 20% of the total pore surface area, atleast 30% of the total pore surface area, at least 40% of the total poresurface area or at least 50% of the total pore surface area.

In another embodiment, the carbon material comprises a fractional poresurface area of pores at or below 100 nm that comprises at least 50% ofthe total pore surface area, at least 75% of the total pore surfacearea, at least 90% of the total pore surface area or at least 99% of thetotal pore surface area. In another embodiment, the carbon materialcomprises a fractional pore surface area of pores at or below 20 nm thatcomprises at least 50% of the total pore surface area, at least 75% ofthe total pore surface area, at least 90% of the total pore surface areaor at least 99% of the total pore surface area.

In another embodiment, the carbon material comprises pores predominantlyin the range of 1000 angstroms or lower, for example 100 angstroms orlower, for example 50 angstroms or lower. Alternatively, the carbonmaterial comprises micropores in the range of 0-20 angstroms andmesopores in the range of 20-300 angstroms. The ratio of pore volume orpore surface in the micropore range compared to the mesopore range canbe in the range of 95:5 to 5:95. Alternatively, the ratio of pore volumeor pore surface in the micropore range compared to the mesopore rangecan be in the range of 20:80 to 60:40.

In other embodiments, the carbon materials are mesoporous and comprisemonodisperse mesopores. As used herein, the term “monodisperse” whenused in reference to a pore size refers generally to a span (furtherdefined as (Dv,90−Dv,10)/Dv, 50 where Dv,10, Dv,50 and Dv,90 refer tothe pore size at 10%, 50% and 90% of the distribution by volume of about3 or less, typically about 2 or less, often about 1.5 or less.

Yet in other embodiments, the carbons materials comprise a pore volumeof at least 1 cc/g, at least 2 cc/g, at least 3 cc/g, at least 4 cc/g orat least 7 cc/g. In one particular embodiment, the carbon materialscomprise a pore volume of from 1 cc/g to 7 cc/g.

In other embodiments, the carbon materials comprise at least 50% of thetotal pore volume residing in pores with a diameter ranging from 50 Å to5000 Å. In some instances, the carbon materials comprise at least 50% ofthe total pore volume residing in pores with a diameter ranging from 50Å to 500 Å. Still in other instances, the carbon materials comprise atleast 50% of the total pore volume residing in pores with a diameterranging from 500 Å to 1000 Å. Yet in other instances, the carbonmaterials comprise at least 50% of the total pore volume residing inpores with a diameter ranging from 1000 Å to 5000 Å.

In some embodiments, the mean particle diameter for the carbon materialsranges from 1 to 1000 microns. In other embodiments the mean particlediameter for the carbon materials ranges from 1 to 100 microns. Still inother embodiments the mean particle diameter for the carbon materialsranges from 1 to 50 microns. Yet in other embodiments, the mean particlediameter for the carbon materials ranges from 5 to 15 microns or from 1to 5 microns. Still in other embodiments, the mean particle diameter forthe carbon materials is about 10 microns. Still in other embodiments,the mean particle diameter for the carbon materials is less than 4, isless than 3, is less than 2, is less than 1 microns.

In some embodiments, the carbon materials exhibit a mean particlediameter ranging from 1 nm to 10 nm. In other embodiments, the meanparticle diameter ranges from 10 nm to 20 nm. Yet in other embodiments,the mean particle diameter ranges from 20 nm to 30 nm. Still in otherembodiments, the mean particle diameter ranges from 30 nm to 40 nm. Yetstill in other embodiments, the mean particle diameter ranges from 40 nmto 50 nm. In other embodiments, the mean particle diameter ranges from50 nm to 100 nm. In other embodiments, the mean particle diameter rangesfrom about 1 μm to about 1 mm. In other embodiments, the mean particlediameter ranges from about 100 μm to about 10 μm. In other embodiments,the mean particle diameter is about 100 μm, about 50 μm or about 10 μm.

In some embodiments, the mean particle diameter for the carbons rangesfrom 1 to 1000 microns. In other embodiments the mean particle diameterfor the carbon ranges from 1 to 100 microns. Still in other embodimentsthe mean particle diameter for the carbon ranges from 5 to 50 microns.Yet in other embodiments, the mean particle diameter for the carbonranges from 5 to 15 microns. Still in other embodiments, the meanparticle diameter for the carbon is about 10 microns.

In some embodiments, the carbon materials exhibit a mean particlediameter ranging from 1 micron to 5 microns. In other embodiments, themean particle diameter ranges from 5 microns to 10 microns. In yet otherembodiments, the mean particle diameter ranges from 10 nm to 20 microns.Still in other embodiments, the mean particle diameter ranges from 20 nmto 30 microns. Yet still in other embodiments, the mean particlediameter ranges from 30 microns to 40 microns. Yet still in otherembodiments, the mean particle diameter ranges from 40 microns to 50microns. In other embodiments, the mean particle diameter ranges from 50microns to 100 microns. In other embodiments, the mean particle diameterranges in the submicron range <1 micron.

In related embodiments, the carbon materials exhibit a mean particlediameter ranging from 0.1 mm micron to 4 mm. In other embodiments, themean particle diameter ranges from 0.5 mm to 4 mm. In yet otherembodiments, the mean particle diameter ranges from 0.5 mm to 3 mm.Still in other embodiments, the mean particle diameter ranges from 0.5mm to 2 mm. In other embodiments, the mean particle diameter ranges from0.5 mm to 1 mm. In certain embodiments, the mean particle diameter isabout 0.9 mm, about 0.8 mm or about 0.5 mm.

In still other embodiments, the carbon materials comprise amonodisperse, or near monodisperse particle size distribution. Forexample, in some embodiments the carbon material has a particle sizedistribution such that (Dv,90−Dv,10)/Dv,50 is less than 3, whereinDv,10, Dv,50 and Dv,90 are the particle size at 10%, 50% and 90%,respectively of the particle size distribution by volume. In furtherembodiments, (Dv,90−Dv,10)/Dv,50 is less than 2 or even less than 1. Instill other embodiments, (Dv,90−Dv,10)/Dv,50 is less than 1,000, lessthan 100, less than 10, less than 5, less than 3, less than 2, less than1.5 or even less than 1.

In yet other embodiments, the carbon materials comprise carbon particleshaving a substantially spherical geometry as determined by opticalmicroscopy and image analysis (see e.g., FIG. 23B). For example, greaterthan 90%, greater than 95% or even greater than 99% of the carbonparticles may have a spherical geometry. Such geometry may improve theperformance of any number of electrical devices comprising the carbonmaterials since the geometry is known to affect particle packing (andthus energy density). In some embodiments, carbon material comprises aplurality of carbon particles, wherein greater than 90% of the carbonparticles have a spherical geometry. For example, in some embodiments,greater than 95% of the carbon particles have a spherical geometry.

As noted above, the presently disclosed methods advantageously providepolymer gels and/or carbon materials having optimized particle sizedistributions. In some embodiments, the particle size distributioncontributes to enhanced packing of the individual polymer or carbonparticles. Enhanced packing of energy storage particles, for examplecarbon particles, can be beneficial for a variety of applications. Forexample, activated carbon materials comprising high surface areas areroutinely used in energy storage devices such as capacitors,particularly supercapacitors. Typically such high-surface area carbonmaterials tend to have low densities, and thus their capacitance on avolume basis (i.e., volumetric capacitance) is relatively low. Forpractical applications, capacitors require both high gravimetric andhigh volumetric capacitance. For devices that are constrained withrespect to size, volumetric capacitance can be increased by more denselypacking the activated carbon particles. Traditional milling of activatedcarbon materials yields powders having a distribution of particle sizesand a wide and random range of structures (i.e., non-spherical particleshapes). These characteristics limit the ability of activated carbonpowders to be densely packed, thus limiting the volumetric capacitancethat can be achieved by the same. Carbon materials having enhancedpacking properties are described herein and in co-pending U.S.application Ser. No. 13/250,430, which is incorporated herein byreference in its entirety for all purposes.

The present inventors have discovered that the density (i.e., particlepacking) of carbon materials can be optimized by preparation accordingto the presently disclosed methods. By controlling the particle sizedistribution of the carbon particles, enhanced packing of the particlescan be achieved. To this end, a number of different models have beenproposed for the optimum packing of multisized particles. Two equationsin this regard are the formulas provided by Furnas (C. C. Furnas,“Grading Aggregates: I”, Ind. Eng. Chem. 23:1052-58, 1931; F. O.Anderegg, “Grading Aggregates: II”, Ind. Eng. Chem. 23:1058-64), andAndreassen (A. H. M. Andreassen and J. Andersen, Kolloid Z. 50:217-228,1931). Furnas' equation assumes the addition of particles of smaller andsmaller size, while Andreassen's equation assumes the addition ofparticles of larger and larger size. Further, since the Furnas equationprovides a theoretical distribution, while that of Andreassen issemi-empirical, the Andreassen equation has been critized for implyingan infinite distribution with no minimum particle size.

To address this shortcoming, a modified equation has been developed thatlinks the Furnas and Andreassen equations, referred to as the “modifiedAndreassen equation” or the “Dinger-Funk equation” (D. R. Dinger and J.E. Funk, Interceram 41(5):332-334, 1992). While the Andreassen equationgives a straight line on a logarithmic plot, the modified Andreasssenequation gives a downward curvature since it takes into account aminimum particle size (d_(m)) of the distribution. The Andreassenequation (1) and the modified Andreassen equation (2) are presentedbelow:

$\begin{matrix}{{CPFT} = {\left( \frac{d}{D} \right)^{q}*100}} & \left( {{Eq}.1} \right)\end{matrix}$ $\begin{matrix}{{CPFT} = {\frac{\left( {d^{q} - d_{m}^{q}} \right)}{\left( {{Dq} - d_{m}^{q}} \right)}*100}} & \left( {{Eq}.2} \right)\end{matrix}$

wherein

CPFT=Cumulative Percent Finer Than (Cumulative Finer Volumedistribution);

d=Particle size;

d_(m)=Minimum particle size of the distribution;

D=Maximum particle size; and

q=Distribution coefficient (“q-value”).

It should be noted that the above minimum particle size distributionsare based on volumes. This requires that mixtures of powders withdifferent densities be converted to volumes in order to give volumepercent. An important feature of the modified Andreassen equation isinfluence of the q-value on packing. By computer simulations, themodified Andreassen equation describes 100% packing density for infinitedistributions when the q-value is 0.37 or lower (D. R. Dinger and J. E.Funk, Interceram 42(3):150-152, 1993). Of course, as has also beendescribed in the art, real-world systems are finite, and thus 100%packing density is only achievable in theory. For q-values about 0.37,some degree of porosity will be present. Thus, for optimum packing theq-value should not exceed 0.37 and typically ranges from 0.30 to 0.37for densely packed materials.

One method for accessing the particle packing properties of a carbonmaterial, or other energy storage material, is to compare a plot of thecumulative finer volume distribution vs. particle size for the carbonmaterial to the modified Andreassen equation curve. The correlationcoefficient (i.e., R value) of the carbon material curve relative to themodified Andreassen equation curve is an indicator of the extent ofpacking optimization within the carbon material. A correlationcoefficient of 1.0 relative to the modified Andreassen equation curvewould indicate that optimum packing of the carbon particles within thecarbon material has been achieved. Accordingly, in one embodiment thepresent methods are useful for preparation of a carbon material (orpolymer gel) comprising a plurality of carbon particles, wherein theplurality of carbon particles comprises a particle size distributionsuch that the equation of a plot of the cumulative finer volumedistribution vs. particle size comprises a correlation coefficient of0.96 or greater relative to the modified Andreassen equation for theparticle size distribution, and wherein the modified Andreassen equationcomprises a q value of 0.3. In other embodiments, the correlationcoefficient of a plot of the cumulative finer volume distribution vs.particle size of carbon materials prepared according to the disclosedmethods comprises a correlation coefficient of 0.90 or greater, 0.95 orgreater, 0.96 or greater, 0.97 or greater, 0.98 or greater, 0.99 orgreater or even 0.995 or greater relative to the modified Andreassenequation for the given particle size distribution.

Another measure of the particle packing properties of an energy storagematerial is the packing ratio when incorporated into an electrode. Whilethis metric may not correlate directly with the data obtained bycomparing the particle size distribution to the modified Andreassenequation, it serves as another means to assess the packing efficiency ofenergy storage particles. The packing ratio is a measure of the densityof the finished electrode compared to the expected density based on themass and volume of the electrode components. A packing ratio of 1.0would indicate that optimized packing has been achieved. A packing ratioof less than one indicates that less than optimum packing has beenachieved, and a packing ratio of greater than one indicates that packingis optimized beyond that expected based on the mass and volume of thecombined electrode components.

In some embodiments, the packing ratio of the disclosed carbon materialseven exceeds 1.0. Such increased packing ratios provide for improvedvolumetric performance relative to carbon materials comprising a lowerpacking ratio. Accordingly, in some embodiments the disclosed carbonmaterials comprise packing ratios of 0.95 or greater, 0.97 or greater,1.0 or greater, 1.05 or greater, 1.10 or greater, 1.15 or greater or1.20 or greater.

In addition to an increased packing ratio, carbon materials preparedaccording to the disclosed methods have advantageously high calendarratios. The calendar ratio is determined as a ratio of the thickness ofan electrode after it is calendared (i.e., rolled flat) compared to thethickness prior to calendaring (after coating and drying). For example,a calendar ratio of 50% indicates the thickness of the electrode hasdecreased by one-half upon calendaring. A higher calendaring ratioallows preparation of electrodes comprising more carbon per unit volume,and hence a higher energy density (i.e., volumetric capacity). Otherknown carbon electrodes materials cannot be calendared to such highcalendar ratios and instead become brittle and delaminate from theelectrode substrate. Accordingly, in some embodiments the presentlydisclosed carbon materials have a calendar ratio of at least 10%, atleast 20%, at least 30%, at least 35%, at least 40%, at least 45%, atleast 50%, at least 55% or at least 60%.

The particle size distribution of the carbon materials is an importantfactor in their electrochemical performance. In some embodiments, carbonmaterials prepared according to the disclosed methods comprise aplurality of carbon particles having particle sizes ranging from about0.01 μm to about 50 μm. In other embodiments, the particle sizedistribution comprises particle sizes ranging from about 0.01 μm toabout 20 μm. For example, in some embodiments the particle sizedistribution comprises particle sizes ranging from about 0.03 μm toabout 17 μm or from about 0.04 μm to about 12 μm. In certain embodimentsof the foregoing, at least 90%, at least 95% or at least 99% of thecarbon particles having particles sizes in the range of about 0.01 μm toabout 50 μm, about 0.01 μm to about 20 μm, about 0.03 μm to about 17 μmor about 0.04 μm to about 12 μm.

In some embodiments, the disclosed methods result in a carbon materialhaving a trimodal particle size distribution. Such trimodal particlesize distributions may contribute to optimal particle packing, and thusenergy density, of the carbon materials. Accordingly, one embodimentprovides a carbon material, and methods for preparation of the same,having a particle size distribution. For example, in some embodimentsthe carbon materials comprise a trimodal particle size distributionhaving first, second and third particle size maxima. The first particlesize maximum may range from about 0.08 μm to about 0.2 μm, for examplefrom about 0.09 μm to about 0.2 μm, from about 0.1 μm to about 0.2 μm orfrom about 0.1 μm to about 0.15 μm. The second particle size maximum mayrange from about 0.8 μm to about 2.0 μm, from about 0.8 μm to about 1.5μm or from about 0.9 μm to about 1.0 μm. The third particle size maximummay range from about 7.0 μm to about 15.0 μm, from about 8.0 μm to about12.0 μm or from about 9.0 μm to about 10.0 μm.

Alternatively, the particle size of the various carbons comprising thehighly packed electrode can be described in terms of their size relativeto the electrode thickness. For instance, a highly packed bimodalparticle distribution comprised of particles with a first collection ofparticles of mean particle size A μm and a second collection ofparticles with mean size B μm and an electrode thickness C μm. In oneembodiment, the particles are comprised such that A:B is between about100:1 and 2:1, for example between about 50:1 and 5:1, for example about10:1; and C:A is between about 2:1 and 100:1, for example between about2:1 and 10:1, for example about 5:1.

In another embodiment, the carbon materials prepared according to thedisclosed methods comprise a highly packed trimodal particledistribution comprised of particles with a first collection of particlesof mean particle size A μm and a second collection of particles withmean size B μm and a third collection of particles with mean size C μmand an electrode thickness D μm. In one embodiment, the particles arecomprised such that A:B and B:C are between about 100:1 and 2:1, forexample between about 50:1 and 5:1, for example about 10:1; and D:A isbetween about 2:1 and 100:1, for example between about 2:1 and 10:1, forexample about 5:1.

Applicants have also discovered the tap density of the carbon materialsprepared according to the disclosed methods to be unexpectedly high. Inthis regard, the high tap densities are also believed to contribute, atleast in part, to the unexpectedly high energy densities of the carbonmaterials. In some embodiments, the disclosed carbon material has a tapdensity between 0.2 and 0.6 g/cc, between 0.3 and 0.5 g/cc or between0.4 and 0.5 g/cc. In another embodiment, the disclosed carbon materialhas a total pore volume of at least 0.5 cm³/g, at least 0.7 cm³/g, atleast 0.75 cm³/g, at least 0.9 cm³/g, at least 1.0 cm³/g, at least 1.1cm³/g, at least 1.2 cm³/g, at least 1.3 cm³/g, at least 1.4 cm³/g, atleast 1.5 cm³/g, at least 1.6 cm³/g, at least 1.7 cm³/g, at least 1.8cm³/g, at least 1.9 cm³/g or at least 2.0 cm³/g.

Applicants have also discovered that the carbon materials describedherein achieve unexpected increase to extremely high carbon surface areaper unit volume. This surface area per unit volume is calculated as theproduct of the carbon specific surface area (for example, as determinedfrom nitrogen sorption methodology) and the tap density. For example,applicants have found that the internal carbon surface area per unitvolume can be increased from about 460 m²/cc to about 840 m²/cc,representing about an 83% increase over other known carbons.

D. Characterization of Polymer Gels and Carbon Materials

The structural properties of the final carbon material and intermediatepolymer gels may be measured using Nitrogen sorption at 77K, a methodknown to those of skill in the art. The final performance andcharacteristics of the finished carbon material is important, but theintermediate products (both dried polymer gel and pyrolyzed, but notactivated, polymer gel), can also be evaluated, particularly from aquality control standpoint, as known to those of skill in the art. TheMicromeretics ASAP 2020 is used to perform detailed micropore andmesopore analysis, which reveals a pore size distribution from 0.35 nmto 50 nm in some embodiments. The system produces a nitrogen isothermstarting at a pressure of 10⁻⁷ atm, which enables high resolution poresize distributions in the sub 1 nm range. The software generated reportsutilize a Density Functional Theory (DFT) method to calculate propertiessuch as pore size distributions, surface area distributions, totalsurface area, total pore volume, and pore volume within certain poresize ranges.

The impurity content of the carbon materials can be determined by anynumber of analytical techniques known to those of skill in the art. Oneparticular analytical method useful within the context of the presentdisclosure is proton induced x-ray emission (PIXE). This technique iscapable of measuring the concentration of elements having atomic numbersranging from 11 to 92 at low ppm levels. Accordingly, in one embodimentthe concentration of impurities present in the carbon materials isdetermined by PIXE analysis.

E. Devices Comprising the Carbon Materials

One embodiment of the present invention is an electrode, or a devicecomprising the same, which comprises the disclosed carbon materials.Useful devices in this regard include, but are not limited to, thedevices described below and in co-pending U.S. application Ser. Nos.12/748,219; 12/897,969; 12/829,282; 13/046,572; 12/965,709; 13/336,975;and 61/585,611, each of which are hereby incorporated by reference intheir entireties.

1. EDLCs

The disclosed carbon materials can be used as electrode material in anynumber of electrical energy storage and distribution devices. One suchdevice is an ultracapacitor. Ultracapacitors comprising carbon materialsare described in detail in co-owned U.S. Pat. No. 7,835,136 which ishereby incorporated in its entirety.

EDLCs use electrodes immersed in an electrolyte solution as their energystorage element. Typically, a porous separator immersed in andimpregnated with the electrolyte ensures that the electrodes do not comein contact with each other, preventing electronic current flow directlybetween the electrodes. At the same time, the porous separator allowsionic currents to flow through the electrolyte between the electrodes inboth directions thus forming double layers of charges at the interfacesbetween the electrodes and the electrolyte.

When electric potential is applied between a pair of electrodes of anEDLC, ions that exist within the electrolyte are attracted to thesurfaces of the oppositely-charged electrodes, and migrate towards theelectrodes. A layer of oppositely-charged ions is thus created andmaintained near each electrode surface. Electrical energy is stored inthe charge separation layers between these ionic layers and the chargelayers of the corresponding electrode surfaces. In fact, the chargeseparation layers behave essentially as electrostatic capacitors.Electrostatic energy can also be stored in the EDLCS through orientationand alignment of molecules of the electrolytic solution under influenceof the electric field induced by the potential. This mode of energystorage, however, is secondary.

EDLCS comprising the disclosed carbon material can be employed invarious electronic devices where high power is desired. Accordingly, inone embodiment an electrode comprising the carbon materials is provided.In another embodiment, the electrode comprises activated carbonmaterial. In a further embodiment, an ultracapacitor comprising anelectrode comprising the carbon materials is provided. In a furtherembodiment of the foregoing, the ultrapure synthetic carbon materialcomprises an optimized balance of micropores and mesopores and describedabove.

The disclosed carbon materials find utility in any number of electronicdevices, for example wireless consumer and commercial devices such asdigital still cameras, notebook PCs, medical devices, location trackingdevices, automotive devices, compact flash devices, mobiles phones,PCMCIA cards, handheld devices, and digital music players.Ultracapacitors are also employed in heavy equipment such as: excavatorsand other earth moving equipment, forklifts, garbage trucks, cranes forports and construction and transportation systems such as buses,automobiles and trains.

In one embodiment, the present disclosure is directed to a devicecomprising the carbon materials described herein, wherein the device isan electric double layer capacitor (EDLC) device comprising:

a) a positive electrode and a negative electrode wherein each of thepositive and the negative electrodes comprise the carbon material;

b) an inert porous separator; and

c) an electrolyte;

wherein the positive electrode and the negative electrode are separatedby the inert porous separator.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric power of at least 5 W/g, at least 10W/g, at least 15 W/g, at least 20 W/g, at least 25 W/g, at least 30 W/g,at least 35 W/g, at least 50 W/g. In another embodiment, anultracapacitor device comprising the carbon material comprises avolumetric power of at least 2 W/g, at least 4 W/cc, at least 5 W/cc, atleast 10 W/cc, at least 15 W/cc or at least 20 W/cc. In anotherembodiment, an ultracapacitor device comprising the carbon materialcarbon material comprises a gravimetric energy of at least 2.5 Wh/kg, atleast 5.0 Wh/kg, at least 7.5 Wh/kg, at least 10 Wh/kg, at least 12.5Wh/kg, at least 15.0 Wh/kg, at least 17.5. Wh/kg, at least 20.0 Wh/kg,at least 22.5 Wh/kg or at least 25.0 Wh/kg. In another embodiment, anultracapacitor device comprising the carbon material comprises avolumetric energy of at least 1.5 Wh/liter, at least 3.0 Wh/liter, atleast 5.0 Wh/liter, at least 7.5 Wh/liter, at least 10.0 Wh/liter, atleast 12.5 Wh/liter, at least 15 Wh/liter, at least 17.5 Wh/liter or atleast 20.0 Wh/liter.

In some embodiments of the foregoing, the gravimetric power, volumetricpower, gravimetric energy and volumetric energy of an ultracapacitordevice comprising the carbon material are measured by constant currentdischarge from 2.7 V to 1.89 V employing a 1.0 M solution oftetraethylammonium-tetrafluroroborate in acetonitrile (1.0 M TEATFB inAN) electrolyte and a 0.5 second time constant.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric power of at least 10 W/g, a volumetricpower of at least 5 W/cc, a gravimetric capacitance of at least 100 F/g(@0.5 A/g) and a volumetric capacitance of at least 10 F/cc (@0.5 A/g).In one embodiment, the aforementioned ultracapacitor device is a coincell double layer ultracapacitor comprising the carbon material, aconductivity enhancer, a binder, an electrolyte solvent, and anelectrolyte salt. In further embodiments, the aforementionedconductivity enhancer is a carbon black and/or other conductivityenhancer known in the art. In further embodiments, the aforementionedbinder is Teflon and or other binder known in the art. In furtheraforementioned embodiments, the electrolyte solvent is acetonitrile orpropylene carbonate, or other electrolyte solvent(s) known in the art.In further aforementioned embodiments, the electrolyte salt istetraethylaminotetrafluroborate or triethylmethyl aminotetrafluroborateor other electrolyte salt known in the art, or liquid electrolyte knownin the art.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric power of at least 15 W/g, a volumetricpower of at least 10 W/cc, a gravimetric capacitance of at least 110 F/g(@0.5 A/g) and a volumetric capacitance of at least 15 F/cc (@0.5 A/g).In one embodiment, the aforementioned ultracapacitor device is a coincell double layer ultracapacitor comprising the carbon material, aconductivity enhancer, a binder, an electrolyte solvent, and anelectrolyte salt. In further embodiments, the aforementionedconductivity enhancer is a carbon black and/or other conductivityenhancer known in the art. In further embodiments, the aforementionedbinder is Teflon and or other binder known in the art. In furtheraforementioned embodiments, the electrolyte solvent is acetonitrile orpropylene carbonate, or other electrolyte solvent(s) known in the art.In further aforementioned embodiments, the electrolyte salt istetraethylaminotetrafluroborate or triethylmethyl aminotetrafluroborateor other electrolyte salt known in the art, or liquid electrolyte knownin the art.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric capacitance of at least 90 F/g, atleast 95 F/g, at least 100 F/g, at least 105 F/g, at least 110 F/g, atleast 115 F/g, at least 120 F/g, at least 125 F/g, or at least 130 F/g.In another embodiment, an ultracapacitor device comprising the carbonmaterial comprises a volumetric capacitance of at least 5 F/cc, at least10 F/cc, at least 15 F/cc, at least 20 F/cc, at least 25 F/cc, or atleast 30 F/cc. In some embodiments of the foregoing, the gravimetriccapacitance and volumetric capacitance are measured by constant currentdischarge from 2.7 V to 0.1 V with a 5-second time constant andemploying a 1.8 M solution of tetraethylammonium-tetrafluroroborate inacetonitrile (1.8 M TEATFB in AN) electrolyte and a current density of0.5 A/g, 1.0 A/g, 4.0 A/g or 8.0 A/g.

In one embodiment, the present disclosure provides ultracapacitorscomprising a carbon material as disclosed herein, wherein the percentdecrease in original capacitance (i.e., capacitance before beingsubjected to voltage hold) of the ultracapacitor comprising the carbonmaterial after a voltage hold period is less than the percent decreasein original capacitance of an ultracapacitor comprising known carbonmaterials. In one embodiment, the percent of original capacitanceremaining for an ultracapacitor comprising the carbon material after avoltage hold at 2.7 V for 24 hours at 65° C. is at least 90%, at least80%, at least 70%, at least 60%, at least 50%, at least 40%, at least30% at least 20% or at least 10%. In further embodiments of theforegoing, the percent of original capacitance remaining after thevoltage hold period is measured at a current density of 0.5 A/g, 1 A/g,4 A/g or 8 A/g.

In another embodiment, the present disclosure provides ultracapacitorscomprising a carbon material as disclosed herein, wherein the percentdecrease in original capacitance of the ultracapacitor comprising thecarbon material after repeated voltage cycling is less than the percentdecrease in original capacitance of an ultracapacitor comprising knowncarbon materials subjected to the same conditions. For example, in oneembodiment, the percent of original capacitance remaining for anultracapacitor comprising the carbon material is more than the percentof original capacitance remaining for an ultracapacitor comprising knowncarbon materials after 1000, 2000, 4000, 6000, 8000, or 1000 voltagecycling events comprising cycling between 2 V and 1V at a currentdensity of 4 A/g. In another embodiment, the percent of originalcapacitance remaining for an ultracapacitor comprising the carbonmaterial after 1000, 2000, 4000, 6000, 8000, or 1000 voltage cyclingevents comprising cycling between 2 V and 1V at a current density of 4A/g, is at least 90%, at least 80%, at least 70%, at least 60%, at least50%, at least 40%, at least 30% at least 20% or at least 10%.

As noted above, the carbon material can be incorporated intoultracapacitor devices. In some embodiments, the carbon material ismilled to an average particle size of about 10 microns using a jetmillaccording to the art. While not wishing to be bound by theory, it isbelieved that this fine particle size enhances particle-to-particleconductivity, as well as enabling the production of very thin sheetelectrodes. The jetmill essentially grinds the carbon against itself byspinning it inside a disc shaped chamber propelled by high-pressurenitrogen. As the larger particles are fed in, the centrifugal forcepushes them to the outside of the chamber; as they grind against eachother, the particles migrate towards the center where they eventuallyexit the grinding chamber once they have reached the appropriatedimensions.

In further embodiments, after jet milling the carbon is blended with afibrous Teflon binder (3% by weight) to hold the particles together in asheet. The carbon Teflon mixture is kneaded until a uniform consistencyis reached. Then the mixture is rolled into sheets using a high-pressureroller-former that results in a final thickness of 50 microns. Theseelectrodes are punched into discs and heated to 195° C. under a dryargon atmosphere to remove water and/or other airborne contaminants. Theelectrodes are weighed and their dimensions measured using calipers.

The carbon electrodes of the EDLCs are wetted with an appropriateelectrolyte solution. Examples of solvents for use in electrolytesolutions for use in the devices of the present application include butare not limited to propylene carbonate, ethylene carbonate, butylenecarbonate, dimethyl carbonate, methyl ethyl carbonate, diethylcarbonate, sulfolane, methylsulfolane and acetonitrile. Such solventsare generally mixed with solute, including, tetralkylammonium salts suchas TEATFB (tetraethylammonium tetrafluoroborate); TEMATFB(tri-ethyl,methylammonium tetrafluoroborate); EMITFB(1-ethyl-3-methylimidazolium tetrafluoroborate), tetramethylammonium ortriethylammonium based salts. Further the electrolyte can be a waterbased acid or base electrolyte such as mild sulfuric acid or potassiumhydroxide.

In some embodiments, the electrodes are wetted with a 1.0 M solution oftetraethylammonium-tetrafluroroborate in acetonitrile (1.0 M TEATFB inAN) electrolyte. In other embodiments, the electrodes are wetted with a1.0 M solution of tetraethylammonium-tetrafluroroborate in propylenecarbonate (1.0 M TEATFB in PC) electrolyte. These are commonelectrolytes used in both research and industry and are consideredstandards for assessing device performance. In other embodiments, thesymmetric carbon-carbon (C—C) capacitors are assembled under an inertatmosphere, for example, in an Argon glove box, and a NKK porousmembrane 30 micron thick serves as the separator. Once assembled, thesamples may be soaked in the electrolyte for about 20 minutes or moredepending on the porosity of the sample.

In some embodiments, the capacitance and power output are measured usingcyclic voltametry (CV), chronopotentiometry (CP) and impedancespectroscopy at various voltages (ranging from 1.0-2.5 V maximumvoltage) and current levels (from 1-10 mA) on a Biologic VMP3electrochemical workstation. In this embodiment, the capacitance may becalculated from the discharge curve of the potentiogram using theformula:

$\begin{matrix}{C = \frac{I \times \Delta t}{\Delta V}} & {{Equation}1}\end{matrix}$where I is the current (A) and ΔV is the voltage drop, Δt is the timedifference. Because in this embodiment the test capacitor is a symmetriccarbon-carbon (C—C) electrode, the specific capacitance is determinedfrom:C _(s)=2C/m _(e)  Equation 2where m_(e) is the mass of a single electrode. The specific energy andpower may be determined using:

$\begin{matrix}{E_{s} = {\frac{1}{4}\frac{CV_{\max}^{2}}{m_{e}}}} & {{Equation}3}\end{matrix}$ $\begin{matrix}{P_{s} = {E_{s}/4ESR}} & {{Equation}4}\end{matrix}$where C is the measured capacitance V_(max) is the maximum test voltageand ESR is the equivalent series resistance obtained from the voltagedrop at the beginning of the discharge. ESR can alternately be derivedfrom impedance spectroscopy.

2. Batteries

The disclosed carbon materials also find utility as electrodes in anynumber of types of batteries. For example, one embodiment is directed toan electrical energy storage device comprising:

a) at least one anode comprising a carbon material;

b) at least cathode comprising a metal oxide; and

c) an electrolyte comprising lithium ions;

wherein the carbon material is any of the carbon materials describedherein.

Another embodiment is directed to a metal air battery, for examplelithium air batteries. Lithium air batteries generally comprise anelectrolyte interposed between positive electrode and negativeelectrodes. The positive electrode generally comprises a lithiumcompound such as lithium oxide or lithium peroxide and serves to oxidizeor reduce oxygen. The negative electrode generally comprises acarbonaceous substance which absorbs and releases lithium ions. As withsupercapacitors, batteries such as lithium air batteries which comprisethe disclosed carbon materials are expected to be superior to batteriescomprising known carbon materials. Accordingly, in one embodiment thepresent invention provides a metal air battery, for example a lithiumair battery, comprising a carbon material as disclosed herein.

Any number of other batteries, for example, zinc-carbon batteries,lithium/carbon batteries, lead acid batteries and the like are alsoexpected to perform better with the carbon materials described herein.One skilled in the art will recognize other specific types of carboncontaining batteries which will benefit from the disclosed carbonmaterials. Accordingly, in another embodiment the present inventionprovides a battery, in particular a zinc/carbon, a lithium/carbonbatteries or a lead acid battery comprising a carbon material asdisclosed herein.

EXAMPLES

The carbon materials disclosed in the following Examples were preparedaccording to the methods disclosed herein. Chemicals were obtained fromcommercial sources at reagent grade purity or better and were used asreceived from the supplier without further purification.

In some examples, the polymer gel particles are freeze dried prior topyrolysis and/or activation. In these examples, the lyophilizer shelfwas generally pre-cooled to −30° C. before loading a tray containing thefrozen polymer hydrogel particles on the lyophilizer shelf. The chamberpressure for lyophilization was typically in the range of 50 to 1000mTorr and the shelf temperature was in the range of +10 to +25° C.Alternatively, the shelf temperature can be set lower, for example inthe range of 0 to +10° C. Alternatively, the shelf temperature can beset higher, for example in the range of 25 to +100° C. Chamber pressurecan be held in the range of 50 to 3000 mTorr. For instance, the chamberpressure can be controlled in the range of 150 to 300 mTorr.

Unless noted otherwise, the polymer was pyrolyzed by heating in anitrogen atmosphere at temperatures ranging from 700-1200° C. for aperiod of time as specified in the examples, for example 850° C. with anitrogen gas flow of 200 L/h. Activation conditions generally comprisedheating a pyrolyzed polymer hydrogel in a CO₂ atmosphere at temperaturesranging from 800-1000° C. for a period of time as specified in theexamples, for example 900° C. under a CO₂ for 660 min. Specificpyrolysis and activation conditions were as described in the followingexamples.

TGA studies were performed using a Mettler Toledo TGA/DSC1 707 N₂/CO₂MX5 system. Pyrolysis and activation was performed using a ThermoScientific, Economy Solid Tube furnace. Surface area and pore volumemeasurements were obtained using a Micromeritics Tristar II BET system.

Example 1 Emulsion Preparation of Dried Polymer Gel

For each sample, two separate solutions were prepared. Five differentgel solutions were made by admixing a resorcinol and formaldehyde (molarratio of resorcinol:formaldehyde=0.5:1) solution with a water/aceticacid solvent (75:25) and adding an ammonium acetate catalyst. The ratiosof the various gel reagents are indicated in Table 1 for the fivesamples. A cyclohexane/SPAN 80 solution was also prepared.

The gel solution was allowed to mix for 10 minutes before it was pouredinto the cyclohexane/SPAN80 solution and the temperature was set to 45°C. After 4 hours at 45° C., the temperature was increased to 65-70° C.and held for 24 hours before the excess cyclohexane was decanted and theresin was placed in a 45° C. oven for 10-20 minutes to dry. Sampleconditions are summarized in Table 1.

TABLE 1 Polymerization Conditions Gel Formulation RF SolutionCyclohexane SPAN80 Sample (Solids/Acid/R:C)* (mL) (mL) (mL) % SPAN80 %Gel** RD-507-1 41/20/25 10 100 0.5 0.5% 10% RD-507-2 33/20/10 10 100 0.50.5% 10% RD-507-3 33/20/25 20 150 1.0 0.7% 13% RD-507-4 41/20/10 50 40020.0 5.0% 13% RD-507-5 33/20/25 30 150 2.0 1.3% 20% *(Solids/Acid/R:C)refers to the solids content in percent (e.g. mass resorcinol andformaldehyde to total mass), percent acid of total liquid (e.g. acidplus water) and R:C is mass ratio of resorcinol to catalyst,respectively. **% Gel = Percent loading of RF (i.e.,resorcinol/formaldehyde) solution in total emulsions/suspensionpolymerization solution (e.g. RF solution and continuous phase)

Example 2 Dried Polymer Gel Data

Nitrogen isotherm, surface area and pore volume data for the dried gelsamples from Example 1 are presented in FIG. 1 and in Table 2. Forcomparative purposes, two carbon samples were prepare as controls viathe general “monolith” approach described in Example 15. ComparativeSample 1 was prepared from a gel formulation having a Solids/Acid/R:Cratio of 40/20/10 and Comparative Sample 2 was prepared from a gelformulation having a Solids/Acid/R:C ratio of 33/20/20. All samplesshowed a lower surface area and pore volume compared to the comparativesamples. While not wishing to be bound by theory, it is thought thatthis decrease is likely due to surfactant in the pores and on thesurface of the gel material, and was expected to be burned off duringpyrolysis. This theory was supported by the ability to activate thepyrolyzed material to a target surface area, pore volume, and P95/P5(i.e., ratio of nitrogen sorbed at 95% partial pressure to that sorbedat 5% partial pressure) at a reasonable activation rate. Thereforecertain properties of the dried gel may not be predictive of theproperties of the final carbon materials.

TABLE 2 Properties of Dried Polymer Gel Samples SSA PV Max Pore Sample(m²/g) (cc/g) P95/P5 Width (Å) RD-507-1 481 0.299 1.77 63 RD-507-2 5830.419 2.15 172 RD-507-3 75 0.059 2.40 100 RD-507-4 72 0.101 5.29 86RD-507-5 325 0.297 2.75 108 Comparative 545 0.327 1.80 59 Sample 1Comparative 625-725 0.98-1.20 4.4-5.5 250 Sample 2

Example 3 Activated Carbon Data

Nitrogen isotherm, surface area, pore volume, and electrochemicaltesting (ECT) data for activated carbon samples (RD-507-3, -4, -5) arepresented in FIG. 2 and in Tables 3 & 4. Samples 3 and 5 were pyrolyzedat 900° C. in a kiln and held for 60 minutes at this temperature andsample 4 was pyrolyzed without any drying step prior to pyrolysis (WetGel—60 minutes at 625° C., unless stated otherwise all other gels werefreeze dried prior to pyrolysis). All three samples were activated at900° C. in a tube furnace (CO₂ atmosphere) to achieve a surface area of1700-1900 m²/g. The isotherm data (FIG. 2 ) shows that all three sampleswere very microporous carbon and had a surface area to pore volumedevelopment comparable to a control carbon material prepared viamonolith techniques. All samples also demonstrate ECT performancecomparable to a comparative carbon prepared via monolith techniques(Comparative Sample 3) (24 F/cc at the time). Although the gelformulations employed (sample RD-507-3, -5) were expected to producemesoporous carbons based on known monolith preparations, all carbonsamples surprisingly showed no mesoporosity in the dried gel oractivated carbon.

TABLE 3 Activated Carbon Surface Area and Pore Volume Gel SSA PV Sample(Solid/Acid/RC) (m²/g) (cc/g) P95/P5 Comparative Sample 3 41/20/25 18470.809 1.20 RD-507-3-PCKf-ACt2 33/20/10 1760 0.734 1.08RD-507-4-DTK-ACt1-2 41/20/10 1731 0.733 1.10 RD-507-5-PCK-ACt1-233/20/25 1928 0.818 1.14

TABLE 4 Activated Carbon Electrochemical Testing Performance GelElectrode −45* Normalized Sample (Solid/Acid/RC) Wt F/cc F/g (Hz) F/ccRD-507-3 33/20/10 22.09 22.0 120.0 0.09 24.0 RD-507-4 41/20/10 15.6923.5 120.0 0.14 25.6 RD-507-5 33/20/25 16.17 23.8 118.2 0.16 23.5*Frequency response = Frequency as calculated from the Bode plot at a45° phase angle

Example 4 Preparation of Dried Polymer Gel

To explore the ability of the present method for preparing carbonmaterials having different pore structure (e.g., mesoporosity), fivepolymerizations were carried out using the general procedures describedin Example 1, except the formulations were as set forth in Table 5. As acontrol, the gel formulation for each for each polymerization was alsoallowed to polymerize under monolith conditions (i.e., as described inExample 15). The control sample for each gel formulation is designatedwith a “C” in Table 6.

TABLE 5 Polymerization Conditions Gel Gel Solution Cyclohexane SPAN80 %% RF Sample Formulation (mL) (mL) (mL) SPAN80 Gel RD-562-1 33/20/100 40200 20 10% 20% RD-562-2 33/10/100 40 200 20 10% 20% RD-562-3 33/20/40040 200 20 10% 20% RD-562-4 33/10/400 40 200 20 10% 20% RD-562-5 33/10/5040 200 2  1% 20%

Example 5 Dried Polymer Gel Data

Nitrogen isotherm, surface area and pore volume data for dried gelsamples prepared according to Example 4 are presented in FIG. 3 and inTable 6. All polymer gels were freeze dried prior to analysis. Allsamples showed a collapsed pore structure and lower SSA compared to amonolith prepared control of a mesoporous carbon(Solid/Acid/R:C=33/20/25, designated “NC2-3” herein) and compared to theindividual control (monolith) gels. As discussed above, the low SSA andPV may be an artifact created by surfactant clogging the pores, whichmay or may not be linked to surfactant loading. Samples 1 and 3 bothused 20% acid content and show a small pore volume contribution from themesopore range. Samples 2 and 4 used 10% acid content and both show mostof their pore volume being attributed to macropores.

Taking into account the contraction of the mesopores in samples 1-4, itwas decided to use less surfactant for sample 5. Low acid (10%) with lowR:C (50:1) was used to achieve mesoporosity with no macro-porosity.Sample 5 shows (FIG. 4 ) a much greater contribution of volume frommesopores and maps closely to the NC2-3 control dried gel. The surfacearea (Table 6) is still lower than the control, but based on activationdata (see below) this may be due more to surfactant rather than thedried gel material.

TABLE 6 Dried Gel Surface Area and Pore Volume Gel SSA PV Sample(Solid/Acid/R:C) (m²/g) (cc/g) P95/P5 RD-562-1 33/20/100 143 0.278 5.77RD-562-1C 33/20/100 633 0.882 4.22 RD-562-2 33/10/100 33 0.153 7.80RD-562-2C 33/10/100 396 1.203 4.95 RD-562-3 33/20/400 137 0.249 5.58RD-562-3C 33/20/400 632 1.198 5.44 RD-562-4 33/10/400 25 0.176 8.83RD-562-4C 33/10/400 469 1.169 3.31 RD-562-5 33/10/50 358 0.755 6.70RD-562-5C 33/10/50 687 1.919 7.06 NC2-3 Control 33/20/25 625-7250.98-1.20 4.4-5.5

Example 6 Activated Carbon Data

The gels dried gels from Example 5 were pyrolyzed and activated. Weightloss upon activation, nitrogen isotherm, surface area, pore volume, andECT data for these activated carbon samples are presented in FIGS. 5 & 6and in Table 7. All samples and their controls were pyrolyzed at 900° C.in a tube furnace using a 5° C./min ramp rate and then held for 60minutes. All Pyrolyzed Carbon (PC) samples were put on for TGA analysisof activation rates at 900° C. Each emulsion PC sample was activated at950° C. in the tube furnace.

TGA data (FIG. 5 ) shows a significant increase in activation rate forthe emulsion samples compared to their control samples. This may be duemore to particle size being very small and not solely due to the amountof porosity. Samples 2 and 4 show an increased activation rate comparedto samples 1 and 3, as indicated by higher N₂ adsorption from the sameactivation conditions, and are more macroporous. Samples 1 and 3 used ahigher acid content and contain more mesopore volume, than otherprotocols and were more collapsed compared to the NC2-3 control (FIG. 6). Although samples 1˜4 were over-activated, their pore development isnot similar to NC2-3 carbon. Samples 1 and 3, that used 20% acid, give amore mesoporous carbon development than the samples that used 10% Acid.

Sample 5 used less surfactant with the intention of creating moremesoporosity and the data for sample 5 shows successful creation ofmesoporosity (see FIG. 7 ). This carbon material shows less of a porecontribution from 100-200 A than the NC2-3 control, but this may not bean issue for electrochemical performance. Thus the described method issuitable for preparation of a mesoporous carbon material.

TABLE 7 Activated Carbon Surface Area and Pore Volume Gel SSA PV Sample(Solid/Acid/R:C) (m²/g) (cc/g) P95/P5 RD-562-1-PCt-ACt2 33/20/100 21221.090 1.37 RD-562-2-PCt-ACt1 33/10/100 2423 1.312 1.42 RD-562-3-PCt-ACt133/20/400 2258 1.125 1.36 RD-562-4-PCt-ACt1 33/10/400 2411 1.777 1.48RD-562-5-PCt-ACt3 33/10/50 1704 1.217 1.88 NC2-3 Control 33/20/25 18001.420 2.04

Example 7 Preparation of Dried Polymer Gel

Ten emulsion polymerizations were performed according to the generalprocedures of Example 1 to explore parameters for preparation of amicroporous carbon material. Control samples (designated with “C” inTable 9) were also prepared using the same gel formulations and allowingthe gel to polymerize in a monolith fashion. Polymerization conditionsare set forth in Table 8.

TABLE 8 Polymerization Conditions Sample % Solids % Acid R:C SPAN 80% %RF Gel RD-538-1 50 10 10 1 20 RD-538-2 41 10 25 1 20 RD-538-3 41 20 1030 20 RD-538-4 41 20 25 1 40 RD-538-5 41 20 10 10 20 RD-538-6 41 10 1010 30 RD-538-7 46 15 15 5 25 RD-538-8 50 10 25 10 30 RD-538-9 50 20 2510 20 RD-538-10 50 20 10 1 30

Example 8 Dried Polymer Gel Data

Nitrogen isotherm, surface area and pore volume data for dried gelsamples of Example 7 are presented in FIG. 8 and in Table 8. Samples 3and 4 did not make processable wet gel so no data was collected forthose samples. All other samples were freeze-dried. DFT pore sizedistributions (FIG. 8 ) show a contraction in pore structure in emulsionsamples vs. their oven-cured control as noted with the other examples.Following from this, the emulsion samples show a lower specific surfacearea and pore volume (Table 9) as compared to their correspondingmonolith control samples.

TABLE 9 Dried Gel Surface Area and Pore Volume Gel (Solid/Acid/R:C/ SSAPV Sample Surfactant/RF) (m²/g) (cc/g) P95/P5 RD-538-1 50/10/10/1/20 1080.086 2.36 RD-538-1C 615 0.543 2.70 RD-538-2 41/10/25/1/20 185 0.1953.08 RD-538-2C 618 0.785 3.80 RD-538-5 41/20/10/10/20 94 0.094 2.84RD-538-5C 509 0.315 1.86 RD-538-6 41/10/10/10/30 233 0.264 3.26RD-538-6C 555 0.479 2.62 RD-538-7 46/15/15/5/25 23 0.026 3.19 RD-538-7C580 0.363 1.86 RD-538-8 50/10/25/10/30 110 0.151 4.01 RD-538-8C 6790.814 3.65 RD-538-9 50/20/25/10/20 54 0.039 2.20 RD-538-9C 660 0.5872.69 RD-538-10 50/20/10/1/30 355 0.234 2.03 RD-538- 646 0.542 2.56 10C

Example 9 Activated Carbon Data and Electrochemical Testing

Nitrogen isotherm, surface area and pore volume data for activatedcarbon samples from Example 8 are presented in FIGS. 9 & 10 and in Table10. Samples were pyrolyzed by rapid (<10 sec from 100° C.-625° C.)insertion at 625° C. in the kiln for 60 minutes. All samples wereactivated in a tube furnace at 900° C. with the goal of achieving1700-1900 m²/g SSA. Isotherm data (FIG. 9 ) and DFT pore sizedistributions (FIG. 10 ) demonstrate the ability of the current emulsionformulations to create a microporous carbon, and in fact only one sample(RD-538-2) exhibited any mesoporosity. Mesopore development in RD-538-2may be due to the low surfactant concentration along with low catalystand low acid content. High surfactant loading, ≥5%, produced similarsurface area, pore volume, and isotherm data for activated carbon,independent of gel formulation. With lower surfactant loading, 1%, thematerial shows more sensitivity to changes in gel formulation.

Electrochemical testing (ECT) data for the activated carbons ispresented in Table 11. Samples were milled in a Fritsch mill and thenrolled into dry electrodes for ECT. Sample 5 recorded adequateperformance compared to current NC2-1Ω carbon at similar activationlevels.

TABLE 10 Activated Carbon Surface Area and Pore Volume Gel(Solid/Acid/R:C/ SSA PV P95/ Sample Surfactant/RF) (m²/g) (cc/g) P5 GM*RD-538-1-PCk-ACt3 50/10/10/1/20 1813 0.756 1.09 24.0 RD-538-2-PCk-ACt441/10/25/1/20 783 0.806 2.69 9.7 RD-538-5-PCk-ACt1 41/20/10/10/25 17800.762 1.12 23.4 RD-538-6-PCk-ACt4 41/10/10/10/30 1736 0.733 1.10 23.7RD-538-7-PCk-ACt3 46/15/15/5/25 2074 0.866 1.12 23.9 RD-538-8-PCk-ACt350/10/25/10/30 1910 0.800 1.11 23.9 RD-538-9-PCk-ACt 50/20/25/10/20 17260.721 1.09 23.9 RD-538-10-PCk-ACt4 50/20/10/1/30 1768 0.735 1.08 24.1*GM = (specific surface area)/(100*PV)

TABLE 11 Activated Carbon Electrochemical Testing Performance Gel(Solid/Acid/R:C/ Sample Surfactant/RF) F/cc F/g R2 −45 MaxRD-538-5-PCk-ACt1 41/20/10/10/20 23.9 114.2 4.63 0.14 23.8RD-538-7-PCk-ACt3 46/15/15/5/25 21.5 121.6 5.54 0.16 23.3

Example 10 Preparation of Dried Polymer Gel

To better understand the relationship between emulsion formulations andprocessing parameters, twelve emulsion polymerization experiments wereperformed according to the general procedures described in Example 1.Certain processing parameters such as stir rate, reaction starttemperature and cure time were varied as summarized in Table 12.

TABLE 12 Polymerization Conditions % % % % RF Start Cure Sample SolidsAcid R:C SPAN80 Gel Temp Time RPM RD-579-1 30 5 50 2 30 45 6 200RD-579-2 50 5 50 0.5 30 70 6 400 RD-579-3 30 5 10 0.5 10 45 6 200RD-579-4 30 20 50 0.5 30 45 12 400 RD-579-5 50 20 10 2 10 45 6 400RD-579-6 50 20 50 0.5 10 45 12 200 RD-579-7 30 20 50 0.5 30 45 12 400RD-579-8 30 5 10 0.5 10 70 12 400 RD-579-9 30 20 10 2 30 70 12 200RD-579-10 30 20 50 2 10 70 6 400 RD-579-11 50 5 10 2 30 45 12 400RD-579-12 50 20 10 0.5 30 70 6 200

Example 11 Dried Polymer Gel Data

Nitrogen isotherm, surface area and pore volume data for dried gelsamples of Example 10 are presented in FIG. 11 and in Table 13. Forcomparative purposes, data for representative microporous andmicro/mesoporous gels (NC2-1Ω) and NC2-3, respectively) prepared viamonolith procedures are also presented in FIG. 11 . It can be seen thatthere is a correlation between surface area and cure time. It is alsoclear that one can obtain a spectrum of dry gels ranging from solelymicroporous to micro/mesoporous, and their resulting carbons are readilyavailable through emulsion polymerization.

TABLE 13 Dry Gel Data Gel (Solid/Acid/R:C/ Sample Surfactant/C:RF) SSAPV P95/P5 GM Fines* RD-579-1 30/5/50/2/30 310 0.893 8.46 3.2 1 RD-579-250/5/50/0.5/30 235 0.166 2.12 12.9 0 RD-579-3 30/5/10/0.5/10 156 0.1593.03 8.9 0 RD-579-4 30/20/50/0.5/30 329 0.276 2.57 10.8 2 RD-579-550/20/10/2/10 174 0.113 2.00 14.0 3 RD-579-6 50/20/50/0.5/10 333 0.2242.03 13.5 2 RD-579-7 30/20/50/0.5/30 322 0.268 2.48 10.9 3 RD-579-830/5/10/0.5/10 414 0.583 4.17 6.5 3 RD-579-9 30/20/10/2/30 286 0.2062.20 12.6 1 RD-579-10 30/20/50/2/10 146 0.187 3.53 7.1 2 RD-579-1150/5/10/2/30 417 0.381 2.72 9.9 1 RD-579-12 50/20/10/0.5/30 58 0.0351.83 15.1 0 NC2-1Ω 40/20/10 545 0.327 1.80 — NA NC2-3 33/20/25 625-7250.98-1.20 4.4-5.5 — NA *Scale of 0-3, 0 = no fine material, 3 = mostfine material

Example 12 Activated Carbon Data

As a means to determine appropriate conditions for preparation of amicroporous carbon material via an emulsion polymerization, the gelsfrom example 10 were pyrolyzed at 625° C. in the kiln for 60 minuteswithout previously drying the material gel. Only select samples weredried and then pyrolyzed. All samples were activated in the tube furnaceat 900° C. with the goal of achieving 1700-1900 m²/g SSA. TGA data wascollected to determine activation rates. Pore volume and pore size datais presented in FIGS. 12-15 . Tables 14-16 present various physical andelectrochemical properties of the carbon materials. As can be seen thefull spectrum of microporous to mesoporous carbon materials havingvarious physical and electrochemical properties can be prepared via thedescribed methods. Samples denoted with “PCt” have been freeze driedprior to pyrolysis, while samples identified as “DTk” have beenpyrolyzed directly from wet gel (i.e., not freeze dried).

TABLE 14 Activated Carbon Data Gel (Solid/Acid/R:C/ SampleSurfactant/C:RF) SSA PV P95/P5 GM RD-579-1-DTk- 30/5/50/2/30 1963 0.8601.16 22.8 ACt1 RD-579-2-DTk- 50/5/50/0.5/30 2062 0.873 1.16 23.6 ACt1RD-579-3-DTk- 30/5/10/0.5/10 1889 0.792 1.11 23.9 ACt1 RD-579-4-DTk-30/20/50/0.5/30 1857 0.797 1.13 23.3 ACt1 RD-579-5-DTk- 50/20/10/2/101722 0.716 1.07 24.1 ACt1 RD-579-6-DTk- 50/20/50/0.5/10 1762 0.738 1.1023.9 ACt1 RD-579-7-DTk- 30/20/50/0.5/30 1713 0.738 1.13 23.2 ACt1RD-579-8-DTk- 30/5/10/0.5/10 1566 0.668 1.09 23.4 ACt1 RD-579-9-DTk-30/20/10/2/30 1836 0.764 1.09 24.0 ACt1 RD-579-10-DTk- 30/20/50/2/101557 0.654 1.08 23.8 ACt1 RD-579-11-DTk- 50/5/10/2/30 1362 0.565 1.0624.1 ACt1 RD-579-12-DTk- 50/20/10/0.5/30 1654 0.767 1.22 21.6 ACt1

TABLE 15 RD-579-DG-PC Activated Carbon Surface Area and Pore Volume Gel(Solid/Acid/R:C/ SSA PV Sample Surfactant/RF) (m²/g) (cc/g) JRI GMRD-579-1-PCt-ACt1 30/5/50/2/30 2146 1.752 2.23 12.2 RD-579-8-PCt-ACt130/5/10/0.5/10 2458 1.343 1.52 18.3 RD-579-11-PCt-ACt1 50/5/10/2/30 20080.905 1.21 22.2

TABLE 16 RD-579 Activated Carbon Electrochemical Testing Performance Gel(Solid/Acid/R:C/ −45* Normalized Sample Surfactant/RF) F/cc F/g R2 (Hz)F/cc RD-579-1-PCt-ACt1 30/5/50/2/30 14.6 127.5 4.80 0.26 14.5RD-579-5-DTk-ACt1 50/20/10/2/10 23.7 119.8 4.82 0.07 25.9 *Frequencyresponse = Frequency as calculated from the Bode plot at a 45° phaseangle

Example 13 Variable Process Parameters

In addition to the above process parameters, polymerizations wereperformed with various surfactants and solvents. For each sample, twoseparate solutions were prepared. A gel solution was made as describedherein, and a continuous phase/surfactant solution was also prepared andthe temperature was increased to 85° C. Once the gel solution was donemixing for 10 minutes, it was poured into the continuousphase/surfactant solution and held for 6 hours at 85° C. The sample wasthen removed and placed in a large beaker to let settle. The excesscontinuous phase was decanted off and then the remaining material wasrinsed with iso-propanol and filtered through a Buchner funnel. Samplesconditions are summarized in Table 17. KSP-1 was created to test theemulsion process with mineral oil as the continuous phase.

TABLE 17 Polymerization Conditions for Example 13 RF Gel FormulationSolution Continuous Phase Surfactant Sample (Solids/Acid/R:C) (mL) (mL)(type/mL) RD-592-1 40/10/10 60 Mineral Oil (200) SPAN80/1 RD-592-230/5/50 60 Mineral Oil (200) SPAN80/4 RD-592-3 40/10/10 60 Mineral Oil(200) SPAN20/1 RD-592-4 40/10/10 60 Xylene (200) SPAN80/1 RD-592-540/20/10 60 Paraffin Oil (200) SPAN80/1 KSP-1 50/5/10 60 Mineral Oil(200) SPAN80/4

Nitrogen isotherm, surface area and pore volume data for the dried gelsamples from Example 13 are presented in FIG. 16 and in Table 18.Samples RD-592-1 and RD-592-3 were not filtered, but rinsed with IPA andlet dry in the hood. While not wishing to be bound by theory, it isthought that this decrease in pore volume is likely due to surfactant inthe pores and on the surface of the gel material, and was expected to beburned off during pyrolysis. This theory was supported by the ability toactivate the pyrolyzed material to a target surface area, pore volume,and P95/P5 (i.e., ratio of nitrogen sorbed at 95% partial pressure tothat sorbed at 5% partial pressure) at a reasonable activation rate.Therefore certain properties of the dried gel may not be predictive ofthe properties of the final carbon materials.

It is important to note the ability of higher solids (>30%) formulationsto produce mesoporous resin in an oil emulsion, which was not seen withthe cyclohexane system. Sample RD-592-5 used the microporous monolithformulation, but in the paraffin oil inverse emulsion a mesoporous resinwas produced. This may be due to controlled temperature profile of theresin as it cures in the oil. Different continuous phases may allow moreor less movement of reagents from one phase to the other, which wouldcontribute to a change in porosity as seen here.

TABLE 18 Dry Gel Surface Area and Pore Volume Fines Gel (Solid/Acid/R:C/SSA PV (0 = coarse Sample Surfactant/RF) (m²/g) (cc/g) JRI 3 = fine)RD-592-1 40/10/10/0.5/30 0.073 0 0 2 RD-592-2 30/5/50/0.5/30 260 0.6427.39 3 RD-592-3 40/10/10/0.5/30 2.5 0.004 5.32 1 RD-592-440/10/10/0.5/30 241 0.211 2.58 1 RD-592-5 40/20/10/0.5/30 371 0.593 4.851

Nitrogen isotherm, surface area, pore volume, and ECT data for RD-592activated carbon samples are presented in FIG. 17 and in Tables 19 & 20.All samples were pyrolyzed at 900° C. in the kiln and held for 60minutes at temperature using the fast pyrolysis technique. Samples 1 and5 were pyrolyzed without drying using the DTk technique. All sampleswere activated at 900° C. in the tube furnaces to achieve a surface areaof 1700-1900 m²/g. TGA data was collected to determine activation rates.The isotherm and DFT data (FIGS. 18 & 19 ) shows the ability to makevarious carbon materials. With low solids and acid content a mesoporouscarbon can be achieved in an oil continuous phase. FIGS. 17 & 18 alsoshow the ability to make carbon with properties of a microporous carbonand a mixed microporous/mesoporous carbon.

ECT performance (Table 20) was measured after Fritsch milling thematerial for 15 minutes. Sample RD-592-2's ECT data showed adequateperformance for a mesoporous carbon compared to current EnerG2'smesoporous product. Sample KSP-1's performance was at the same level ascurrent EnerG2's microporous carbon. RD-592-1 produced a device withexceptional energy density.

TABLE 19 RD-592 Activated Carbon Surface Area and Pore Volume Gel(Solid/Acid/R:C/ SSA PV Sample Surfactant/RF) (m²/g) (cc/g) JRIRD-592-1-PCk-ACt2 40/10/10/0.5/30 1628 0.714 1.13 RD-592-2-PCk-ACt230/5/50/0.5/30 1699 1.066 1.64 RD-592-3-PCk-ACt1 40/10/10/0.5/30 16860.758 1.19 RD-592-5-PCk-ACt1 40/20/10/0.5/30 1683 0.752 1.18KSP-1-DTk-ACt2 50/5/10/3/30 2086 0.877 1.15

TABLE 20 RD-592 Activated Carbon Electrochemical Testing Performance Gel(Solid/Acid/R:C/ −45* Normalized Sample Surfactant/RF) F/cc F/g R2 (Hz)F/cc RD-592-1-PCk-ACt2 40/10/10/0.5/30 24.8 114.5 5.95 0.11 25.1RD-592-2-PCk-ACt2 30/5/0/0.5/30 14.1 115.4 7.26 0.26 19.2 KSP-1-DTk-ACt250/5/10/2/30 21.3 122.8 5.93 0.14 23.3 *Frequency response = Frequencyas calculated from the Bode plot at a 45° phase angle

Example 14 Preparation of Phenol Formaldehyde Based Gel

Five different gel solutions were made by admixing a phenol andformaldehyde (molar ratio of phenol:formaldehyde=0.5:1) solution with awater/acid solvent. In some cases an ammonium acetate catalyst wasadded. The ratios of the various gel reagents are indicated in Table 21for the five samples. The gel solution was allowed to mix for 5-10minutes before it was poured into the cyclohexane/SPAN80 solution andthe temperature was set to 95° C. and held for 3-5 days before theexcess continuous phase was decanted. Wet gel samples were pyrolyzeddirectly at 625° C. for 1 hour with weight loss between 50-75%.Representative carbonization and activation data is presented in Table22.

TABLE 21 Gel Preparation Parameters Phenol- Acid Catalyst Water-Acid-Continuous SPAN80 Sample type (g) Formaldehyde¹ Phase (mL) (mL) RD-589-1acetic 20-0 10-30-27 Xylenes 200 5 RD-589-2 acetic 20-0 10-30-27Parrafin oil 5 200 RD-589-3 Oxalic² 20-1 10-2-27 Xylenes 200 5 RD-589-4Acetic 20-0 10-30-27 Parrafin oil 5 200 RD-589-5 Acetic 20-0 10-25-27Parrafin oil 5 200 ¹Added in the form of a 37 wt % aqueous solution²Added in the form of a 5 wt % aqueous solution

TABLE 21 Carbonization and Activation Data TGA activation Surface PoreCarbonization rate (% wt Area Volume Sample wt loss (%) loss/min) (m²/g)(cc/g) F/cc F/g ~45 Hz RD-589-4 55 0.187 2209 0.972 1/14 1/14 1/14 *Frequency response = Frequency as calculated from the Bode plot at a 45°phase angle

Example 15 Surfactant-Free Emulsion Urea-Formaldehyde Synthesis

Microspheres of polymer gel can also be created through polymerizationusing an ultra-dilute solution. Polymer gels were prepared using thefollowing general procedure. Urea and formaldehyde (1.6:1) were mixedinto deionized water (143:1 water:urea) at room temperature, forming adilute solution. The solution was mixed for 5 minutes, wherein formicacid is added. After about 30 minutes, the solution turned from clear tomilky white, at which point the solution was allowed to sit, undisturbeduntil a collection of white polymer spheres were formed. In oneembodiment, the specific surface area and pore volume as measured bynitrogen sorption for the polymer spheres is about 7.86 m²/g and about0.57 cm³/g, respectively. In some embodiments the ratio ofurea:formaldehyde, urea:water, quantity of formic acid, dwell and stirtime, and base or acid catalyst can be altered to yield a preferredpolymer.

Polymers were then pyrolyzed to carbon in a kiln at 900° C., at a ramprate of 20° C./min, with a dwell time of 1 hour. In one embodiment, thephysical properties of the carbon after pyrolysis are a surface area ofabout 48.3 m²/g and a pore volume of about 0.036 cm³/g. FIG. 19 showsthe TGA for one embodiment of urea-formaldehyde polymer emulsion. Noticethere a rapid weight loss >90% occurs at the dwell temperature.

The carbon was tested in a lithium ion battery as a hard carbon anodematerial with lithium metal as a counter electrode, 1M LiPF₆ in 1:1ethylene carbon/diethylcarbonate (EC:DEC) as the electrolyte, with acommercial polypropylene separator. In one exemplary embodiment, theelectrochemical performance, shown in FIG. 20 with an 88:2:10 (hardcarbon:carbon black, PVDF binder) composition, displays high gravimetriccapacity (>500 mAh/g).

Example 16 Preparation of Silicon-Carbon Composite

A solution was prepared of resorcinol and formaldehyde (0.5:1 molarratio) in water and acetic acid (40:1 molar ratio) and ammonium acetate(10:1 molar ratio resorcinol to ammonium acetate). Lastly, 1 molarequivalent (resorcinol to silicon) of micronized (−325 mesh) siliconpowder was added to the mixture. The final mixture was stirred for fiveminutes followed by sonication for 10 minutes. This mixture was pouredinto a 1:100 by volume solution of SPAN 80 (surfactant) in cyclohexaneand heated to 45° C. After five hours the temperature was increased to65° C. and allowed to stir (covered) for 24 hours. Once the powdersettled from solution, the cyclohexane was decanted and the recoveredpowder was dried at 88° C. for 10 minutes then pyrolyzed at 650° C. innitrogen flow for 1 hour. The obtained powder had a surface area of 476m2/g, pore volume of 0.212 cm³/g and average pore width of 17.8angstroms.

Voltage vs. specific capacity of the Si—C composite material was testedand results are shown in FIG. 21 . Cells were tested using lithium metalas the counter electrode and the working electrode comprised of 88:2:10by weight Si—C composite material—conductivity enhancer (Super P)—binder(polyvinylidene fluoride). The electrodes were separated by a Rayon 33micron membrane and the electrolyte was 1M LiPF₆ in 1:1 by weightethylene carbonate-diethylene carbonate. The cells were first dischargedto 0.005V at constant current of 40 mA/g and then charged to 2V at thesame current.

Example 17 Particle Size Distribution and Shape

Emulsion polymerizations were performed as described above and activatedcarbon particles prepared. FIG. 22 demonstrates the near monodisperseparticle size distribution for wet gel, dry gel and activated carbonparticles obtained via emulsion polymerization (RD-507-3 wet gelparticles, dry gel particles and activated carbon particles,respectively from left to right). Emulsion formulations and processparameters (e.g., stirring rate, etc.) are modified to control theparticle size and extent of mono-dispersity of the resulting products.FIGS. 23A and 23B demonstrate the spherical nature of the gel and carbonparticles, respectively. The spherical shape has advantages in certainelectrochemical applications where packing of carbon particles affectsthe electrochemical performance of the device.

Example 18 Exemplary Monolith Preparation of Gels and Carbon Materials

A polymer gel was prepared by polymerization of resorcinol andformaldehyde (0.5:1) in a water/acetic acid solvent (75:25) in thepresence of ammonium acetate catalyst. The resorcinol to solvent ration(R/S) was 0.3, and the resorcinol to catalyst ratio (R/C) was 25. Thereaction mixture was placed at elevated temperature (incubation at 45°C. for about 6 h followed by incubation at 85° C. for about 24 h) toallow for gellation to create a polymer gel. Polymer gel particles werecreated from the polymer gel and passed through a 4750 micron meshsieve. The sieved particles were flash frozen by immersion in liquidnitrogen, loaded into a lyophilization tray at a loading of 3 to 7g/in², and lyophilized at approximately 50 mTorr. The time to dry (asinferred from time for product to reach within 2° C. of shelftemperature) varied with product loading on the lyophilizer shelf.

Other monolith gels and carbon materials are prepared according to theabove general procedures. Modifications to the procedure, includingdifferent gel formulations and/or no freeze drying are also used.

Example 19 General Testing of Electrochemical Properties

The carbon samples were analyzed for their electrochemical performance,specifically as an electrode material in EDLC coin cell devices.Specific details regarding fabrication of electrodes, EDLCs and theirtesting are described below.

Capacitor electrodes comprised about 97 parts by weight carbon particles(average particle size 5-15 microns) and about 3 parts by weight Teflon.The carbon and Teflon were masticated in a mortar and pestle until theTeflon was well distributed and the composite had some physicalintegrity. After mixing, the composite was rolled out into a flat sheet,approximately 50 microns thick. Electrode disks, approximately 1.59 cmin diameter, were punched out of the sheet. The electrodes were placedin a vacuum oven attached to a dry box and heated for 12 hours at 195°C. This removed water adsorbed from the atmosphere during electrodepreparation. After drying, the electrodes were allowed to cool to roomtemperature, the atmosphere in the oven was filled with argon and theelectrodes were moved into the dry box where the capacitors were made.

A carbon electrode was placed into a cavity formed by a 1 inch (2.54 cm)diameter carbon-coated aluminum foil disk and a 50 micron thickpolyethylene gasket ring which had been heat sealed to the aluminum. Asecond electrode was then prepared in the same way. Two drops ofelectrolyte comprising 1.8 M tetraethylene ammonium tetrafluoroborate inacetonitrile were added to each electrode. Each electrode was coveredwith a 0.825 inch diameter porous polypropylene separator. The twoelectrode halves were sandwiched together with the separators facingeach other and the entire structure was hot pressed together.

When complete, the capacitor was ready for electrical testing with apotentiostat/function generator/frequency response analyzer. Capacitancewas measured by a constant current discharge method, comprising applyinga current pulse for a known duration and measuring the resulting voltageprofile. By choosing a given time and ending voltage, the capacitancewas calculated from the following C=It/ΔV, where C=capacitance,I=current, t=time to reached the desired voltage and ΔV=the voltagedifference between the initial and final voltages. The specificcapacitance based on the weight and volume of the two carbon electrodeswas obtained by dividing the capacitance by the weight and volumerespectively. This data is reported for discharge between 2.43 and1.89V.

Example 20 Electrochemical Stability of the Carbons

The follow example illustrates how the electrochemical stability can bemeasured. (physicochemical properties of one of the test carbons isdescribed in the table below).

Test Result Particle Size Dv, 100 20.6 um Dv, 99 17.6 um Dv, 50 7.4 umDv, 1 1.1 um Tap Density 0.52 g/cm3 Specific Surface Area 1709 m2/gTotal Pore Volume 0.710 cm3/g GM (SSA/PV) 0.710 cm3/g PIXE (PurityAnalysis) Calcium = 4.664 ppm Iron = 2.512 ppm Nickel = 1.345 ppm Allother elements not detected

In this case, the electrochemical performance was measured in terms ofcapacitance retention after exposure to high temperature at voltagehold. Specifically, this carbon was processed at pilot scale intoelectrodes produced via aqueous slurry processing of a 95:5:3carbon:carbon black: styrene-butadiene copolymer mixture according tomethods known in the art, and the electrodes were assembled into 100 Felectric double layer capacitors with 1 M tetraethylammoniumtetrafluoroborate in acetonitrile solvent employing methods known in theart. The ultracapacitors were subjected to incubation at 85 C and heldunder a voltage of 2.85 V. Following incubation at this condition for 32hours, this device was cooled to room temperature within 1 hour andmeasured for its capacitance retention. The capacitance retention wasfound to retain 91.2% of the original capacitance, compared to a controlcase for a 100 F commercially available ultracapacitor produced from acommercial carbon which was found under the same conditions to exhibit amaximum theoretical capacitance of 19.9 F/cc, corresponding to 90.4% ofits original capacitance.

Based on the above data, and without being bound by theory, thetechniques described herein to produce carbon with a maximum theoreticalcapacitance of greater than 26 F/cc would result in a carbon withgreater than 23.7 F/cc after 32 hour exposure to 2.85 V hold and 85 C.Additionally, the techniques described herein to produce carbon with amaximum theoretical capacitance of greater than 27 F/cc would result ina carbon with greater than 24.6 F/cc after 32 hour exposure to 2.85 Vhold and 85 C.

The various embodiments described above can be combined to providefurther embodiments. All of the U.S. patents, U.S. patent applicationpublications, U.S. patent applications, foreign patents, foreign patentapplications and non-patent publications referred to in thisspecification and/or listed in the Application Data Sheet, areincorporated herein by reference, in their entirety. Aspects of theembodiments can be modified, if necessary to employ concepts of thevarious patents, applications and publications to provide yet furtherembodiments. These and other changes can be made to the embodiments inlight of the above-detailed description. In general, in the followingclaims, the terms used should not be construed to limit the claims tothe specific embodiments disclosed in the specification and the claims,but should be construed to include all possible embodiments along withthe full scope of equivalents to which such claims are entitled.Accordingly, the claims are not limited by the disclosure.

The invention claimed is:
 1. A battery electrode composition comprisinga plurality of composite particles having an average particle size,Dv,50, of less than 1 mm and wherein individual composite particlescomprise: (a) a carbon material comprising: (i) a pore structure havingmicropores and mesopores, (ii) a maximum theoretical capacitance greaterthan 25 F/cm³ as measured at a current density of 0.5 Amp/g employing anelectrolyte comprising tetraethylammonium tetrafluoroborane inacetonitrile, (iii) a BET specific surface area of at least 500 m²/g,and (iv) less than 500 ppm of all atoms having a molecular weightbetween 11 and 92, as measured by photon induced x-ray emissions; and(b) an electrochemical modifier incorporated within the pore structureof the carbon material, wherein the electrochemical modifier comprisessilicon in elemental form.
 2. The battery electrode composition of claim1, wherein the carbon material further comprises a total pore volume ofat least 0.5 cc/g.
 3. The battery electrode composition of claim 1,wherein the carbon material is electrically conductive.
 4. The batteryelectrode composition of claim 1, wherein a content of theelectrochemical modifier in the composite particles is at least 25% to95% weight percent.
 5. The battery electrode composition of claim 1,wherein the carbon material further comprises at least 0.1 cc/g of poreswith a pore size greater than 20 Angstroms.
 6. The battery electrodecomposition of claim 1, wherein the composite particles further comprisegreater than 100 ppm of the electrochemical modifier.
 7. The batteryelectrode composition of claim 1, wherein the carbon material furthercomprises a peak pore volume ranging from 2 to 100 nm.
 8. The batteryelectrode of claim 1, wherein the carbon material further comprises aBET specific surface area of at least 1000 m²/g.
 9. The batteryelectrode of claim 1, wherein the carbon material further comprises atap density of at least 0.3 g/cc.
 10. A battery, comprising an anode andcathode, wherein the anode comprises the battery electrode compositionof claim
 1. 11. A battery electrode composition comprising a pluralityof composite particles having an average particle size, Dv,50, of lessthan 1 mm and wherein individual composite particles comprise: (a) acarbon material comprising: (i) a pore structure having micropores andmesopores, (ii) a maximum theoretical capacitance greater than 25 F/cm³as measured at a current density of 0.5 Amp/g employing an electrolytecomprising tetraethylammonium tetrafluoroborane in acetonitrile, (iii).a total pore volume of at least 0.7 cm³/g, and (iv) less than 500 ppm ofall atoms having a molecular weight between 11 and 92, as measured byphoton induced x-ray emissions; and (b) an electrochemical modifierincorporated within the pore structure of the carbon material, andwherein the electrochemical modifier comprises silicon in elementalform.
 12. The battery electrode composition of claim 11, wherein thecarbon material comprises a total pore volume of at least 0.9 cm³/g. 13.The battery electrode composition of claim 11, wherein the carbonmaterial is electrically conductive.
 14. The battery electrodecomposition of claim 11, wherein a content of the electrochemicalmodifier in the composite particles is at least 25% to 95% weightpercent.
 15. The battery electrode composition of claim 11, wherein thecarbon material further comprises at least 0.1 cc/g of pores with a poresize greater than 20 Angstroms.
 16. The battery electrode composition ofclaim 11, wherein the composite particles further comprise greater than100 ppm of the electrochemical modifier.
 17. The battery electrodecomposition of claim 11, wherein the carbon material further comprises apeak pore volume ranging from 2 to 100 nm.
 18. The battery electrode ofclaim 11, wherein the carbon material further comprises a BET specificsurface area of at least 400 m²/g.
 19. The battery electrode of claim11, wherein the carbon material further comprises a tap density of atleast 0.3 g/cc.
 20. A battery comprising an anode and cathode, whereinthe anode comprises the battery electrode composition of claim 11.